Science of Synthesis: Houben-Weyl Methods of Molecular Transformations  Vol. 7 -  - E-Book

Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 7 E-Book

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Science of Synthesis provides a critical review of the synthetic methodology developed from the early 1800s to date for the entire field of organic and organometallic chemistry. As the only resource providing full-text descriptions of organic transformations and synthetic methods as well as experimental procedures, Science of Synthesis is therefore a unique chemical information tool. Over 1000 world-renowned experts have chosen the most important molecular transformations for a class of organic compounds and elaborated on their scope and limitations. The systematic, logical and consistent organization of the synthetic methods for each functional group enables users to quickly find out which methods are useful for a particular synthesis and which are not. Effective and practical experimental procedures can be implemented quickly and easily in the lab. // The content of this e-book was originally published in July 2004.

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Science of Synthesis

Science of Synthesis is the authoritative and comprehensive reference work for the entire field of organic and organometallic synthesis.

Science of Synthesis presents the important synthetic methods for all classes of compounds and includes:

Methods critically evaluated by leading scientists

Background information and detailed experimental procedures

Schemes and tables which illustrate the reaction scope

Preface

As our understanding of the natural world increases, we begin to understand complex phenomena at molecular levels. This level of understanding allows for the design of molecular entities for functions ranging from material science to biology. Such design requires synthesis and, as the structures increase in complexity as a necessity for specificity, puts increasing demands on the level of sophistication of the synthetic methods. Such needs stimulate the improvement of existing methods and, more importantly, the development of new methods. As scientists confront the synthetic problems posed by the molecular targets, they require access to a source of reliable synthetic information. Thus, the need for a new, comprehensive, and critical treatment of synthetic chemistry has become apparent. To meet this challenge, an entirely new edition of the esteemed reference work Houben–Weyl Methods of Organic Chemistry will be published starting in the year 2000.

To reflect the new broader need and focus, this new edition has a new title, Science of Synthesis, Houben–Weyl Methods of Molecular Transformations. Science of Synthesis will benefit from more than 90 years of experience and will continue the tradition of excellence in publishing synthetic chemistry reference works. Science of Synthesis will be a balanced and critical reference workproduced by the collaborative efforts of chemists, from both industry and academia, selected by the editorial board. All published results from journals, books, and patent literature from the early 1800s until the year of publication will be considered by our authors, who are among the leading experts in their field. The 48 volumes of Science of Synthesis will provide chemists with the most reliable methods to solve their synthesis problems. Science of Synthesis will be updated periodically and will become a prime source of information for chemists in the 21st century.

Science of Synthesis will be organized in a logical hierarchical system based on the target molecule to be synthesized. The critical coverage of methods will be supported by information intended to help the user choose the most suitable method for their application, thus providing a strong foundation from which to develop a successful synthetic route. Within each category of product, illuminating background information such as history, nomenclature, structure, stability, reactivity, properties, safety, and environmental aspects will be discussed along with a detailed selection of reliable methods. Each method and variation will be accompanied by reaction schemes, tables of examples, experimental procedures, and a background discussion of the scope and limitations of the reaction described.

The policy of the editorial board is to make Science of Synthesis the ultimate tool for the synthetic chemist in the 21st century.

We would like to thank all of our authors for submitting contributions of such outstanding quality, and, also for the dedication and commitment they have shown throughout the entire editorial process.

The Editorial Board

October 2000

D. Bellus (Basel, Switzerland)

E. N. Jacobsen (Cambridge, USA)

S. V. Ley (Cambridge, UK)

R. Noyori (Nagoya, Japan)

M. Regitz (Kaiserslautern, Germany)

P. J. Reider (New Jersey, USA)

E. Schaumann (Clausthal-Zellerfeld, Germany)

I. Shinkai (Tsukuba, Japan)

E. J. Thomas (Manchester, UK)

B. M. Trost (Stanford, USA)

Volume Editor’s Preface

This volume of Science of Synthesis is concerned with the organometallic, metalloorganic, and organic chemistry of the elements in groups 13 and 2 with the exception of boron, which will be discussed thoroughly in Volume 6 of Science of Synthesis.

The chemistry of these main group organometallics and metalloorganics has been studied over a long period of time. However, the most important achievements have occurred rather recently. In fact, recent advances in various analytical technologies have allowed us to understand details of many reactions involving these classical reagents. In light of the clear elucidation of various mechanisms, we now recognize the real role and usage of these metal reagents to be even greater than first anticipated many years ago.

The structure of this volume follows that established in the other organometallic volumes of Science of Synthesis, i. e. the material is organized into methods for the synthesis of the product class in question, with each method usually including a discussion of the scope of the method, examples, and an experimental procedure. The product classes are ordered according to the Science of Synthesis guidelines. A further section titled Applications [of the Product Class] in Organic Synthesis is utilized when the product class is employed as a reagent or catalyst in organic transformations. Synthetically important but uncharacterized complexes are also described in this section.

Finally, I should like to thank everyone who has contributed to this volume, in particular Dr. Joe P. Richmond for his great help at the planning stage of this volume. I am most grateful to the authors for their willingness to devote their time and effort to provide us with these valuable contributions. I would also like to thank Ms Kayo Ota for various secretarial workrelated to this volume. Finally, I gratefully acknowledge the efforts of Dr. M. Fiona Shortt de Hernandez and Dr. Claire Twomey and the team at Thieme for their support, patience, and hard workduring the course of this project.

Volume Editor

Chicago, May 2004

Hisashi Yamamoto

Volume 7: Compounds of Groups 13 and 2 (Al, Ga, In, Tl, Be ••• Ba)

Introduction

H. Yamamoto

7.1 Product Class 1: Aluminum Compounds

7.1.1 Product Subclass 1: Zerovalent Aluminum and Its Alloys

S. Saito

7.1.2 Product Subclass 2: Aluminum Hydrides

S. Saito

7.1.3 Product Subclass 3: Aluminum Halides

S. Saito

7.1.4 Product Subclass 4: Aluminum Alkoxides and Phenoxides

T. Ooi and K. Maruoka

7.1.5 Product Subclass 5: Aluminum Thiolates

T. Ooi and K. Maruoka

7.1.6 Product Subclass 6: Aluminum Selenolates

T. Ooi and K. Maruoka

7.1.7 Product Subclass 7: Aluminum Amides

T. Ooi and K. Maruoka

7.1.8 Product Subclass 8: Aluminum Oxide (Alumina)

S. Tsuboi

7.1.9 Product Subclass 9: Triorganoaluminum Compounds Involving Aluminum Alkyls, Alkenyls, Aryls, and Cyanides

M. Oishi

7.2 Product Class 2: Gallium Compounds

M. Yamaguchi

7.3 Product Class 3: Indium Compounds

T.-P. Loh

7.4 Product Class 4: Thallium Compounds

I. E. Markó

7.5 Product Class 5: Beryllium Compounds

H. Yasuda

7.6 Product Class 6: Magnesium Compounds

7.6.1 Product Subclass 1: Magnesium Metal

J.-H. Zhang, C. C. K. Keh, and C.-J. Li

7.6.2 Product Subclass 2: Magnesium Hydride

J.-H. Zhang, C. C. K. Keh, and C.-J. Li

7.6.3 Product Subclass 3: Magnesium–Metal Reagents

J.-H. Zhang, C. C. K. Keh, and C.-J. Li

7.6.4 Product Subclass 4: Alkynyl Grignard Reagents

A. Yanagisawa

7.6.5 Product Subclass 5: Aryl Grignard Reagents

A. Yanagisawa

7.6.6 Product Subclass 6: Alkenyl Grignard Reagents

A. Yanagisawa

7.6.7 Product Subclass 7: Propargylic Grignard Reagents

A. Yanagisawa

7.6.8 Product Subclass 8: Benzylic Grignard Reagents

A. Yanagisawa

7.6.9 Product Subclass 9: Allylic Grignard Reagents

A. Yanagisawa

7.6.10 Product Subclass 10: Alkyl Grignard Reagents

K. Oshima

7.6.11 Product Subclass 11: Grignard Reagents with Transition Metals

T. Takahashi and Y. Liu

7.6.12 Product Subclass 12: Magnesium Halides

M. Shimizu

7.6.13 Product Subclass 13: Magnesium Oxide, Alkoxides, and Carboxylates

M. Shimizu

7.6.14 Product Subclass 14: Magnesium Amides

M. Shimizu

7.6.15 Product Subclass 15: Dialkyl- and Diarylmagnesiums

J.-H. Zhang, C. C. K. Keh, and C.-J. Li

7.7 Product Class 7: Calcium Compounds

K. Mochida

7.8 Product Class 8: Strontium Compounds

N. Miyoshi

7.9 Product Class 9: Barium Compounds

A. Yanagisawa

Keyword Index

Author Index

Abbreviations

Table of Contents

Introduction

H. Yamamoto

Introduction

7.1 Product Class 1: Aluminum Compounds

7.1.1 Product Subclass 1: Zerovalent Aluminum and Its Alloys

S. Saito

7.1.1 Product Subclass 1: Zerovalent Aluminum and Its Alloys

Synthesis of Product Subclass 1

7.1.1.1 Method 1: Aluminum Treated with Mercury(II)Chloride

7.1.1.2 Method 2: Aluminum Treated with Potassium Hydroxide in Methanol

7.1.1.3 Method 3: Aluminum as Reductant for Titanium(IV)Chloride

7.1.1.4 Method 4: Aluminum–Lead System

7.1.1.5 Method 5: Aluminum–Vanadium–Chlorosilane Combination

7.1.1.6 Method 6: Aluminum–Nickel(II) Chloride System

7.1.1.7 Method 7: Aluminum Activated by an Aqueous Fluoride Salt

7.1.1.8 Method 8: Aluminum–Cobalt Alloy

7.1.1.9 Method 9: Aluminum–Nickel Alloy

7.1.1.10 Method 10: Activated Aluminum by Reduction of Aluminum Halides

7.1.1.11 Method 11: Aluminum–Tin(II) Chloride System

7.1.2 Product Subclass 2: Aluminum Hydrides

S. Saito

7.1.2 Product Subclass 2: Aluminum Hydrides

Synthesis of Product Subclass 2

7.1.2.1 Method 1: Lithium Aluminum Hydride from Lithium Hydride and Aluminum Trichloride

7.1.2.2 Method 2: Magnesium and Calcium Aluminum Hydride from Lithium or Sodium Aluminum Hydride

7.1.2.3 Method 3: Lithium Aluminum Hydride with Copper Salts

7.1.2.3.1 Variation 1: Lithium Aluminum Hydride with Copper(II) Chloride for Reductive Fission of Sulfides

7.1.2.3.2 Variation 2: Lithium Aluminum Hydride with Copper(I) Iodide for Conjugate Reduction of α,β -Unsaturated Carbonyl Compounds

7.1.2.3.3 Variation 3: Lithium Aluminum Hydride with Copper(I) Cyanide for 1, 4-Reduction of an Oxaspirene

7.1.2.4 Method 4: Lithium Aluminum Hydride with Titanium Compounds

7.1.2.4.1 Variation 1: Lithium Aluminum Hydride with Titanium(III) Chloride for Reductive Self-Coupling of Carbonyl Compounds

7.1.2.4.2 Variation 2: Lithium Aluminum Hydride with Titanium(IV) Iodide for the Preparation of α,α-Disubstituted Acetic Acids from Ketones

7.1.2.4.3 Variation 3: Lithium Aluminum Hydride with Dichlorobis(η5-cyclopentadienyl)titanium(IV) for the Dehydroxylation of Allylic Alcohols

7.1.2.4.4 Variation 4: Lithium Aluminum Hydride with Titanium(IV) Chloride for the Deoxygenation of N-Oxides

7.1.2.4.5 Variation 5: Lithium Aluminum Hydride with Titanium(IV) Chloride for the Preparation of Lithium Alkylaluminates from Alkenes

7.1.2.5 Method 5: Lithium Aluminum Hydride with Various Metal Chloride Salts for the Catalytic Reduction of Alkynes, Alkenes, and Aryl and Alkyl Chlorides

7.1.2.6 Method 6: Lithium Aluminum Hydride with Nickel Compounds for Desulfurization Reactions

7.1.2.7 Method 7: Lithium Aluminum Hydride with Zirconium Compounds

7.1.2.7.1 Variation 1: Lithium Aluminum Hydride with Zirconium(IV) Compounds for Hydroaluminations of Alkenes

7.1.2.7.2 Variation 2: Use of Lithium Aluminum Hydride for the Preparation of Bis(η5-cyclopentadienyl)(hydrido)zirconium(IV) Complexes

7.1.2.8 Method 8: Lithium Aluminum Hydride with Boron Trifluoride

7.1.2.9 Method 9: Lithium Aluminum Hydride with Iron Compounds

7.1.2.9.1 Variation 1: Lithium Aluminum Hydride and Dodecacarbonyltriiron(0) for the Reductive Dimerization of α,β -Unsaturated Ketones

7.1.2.9.2 Variation 2: Lithium Aluminum Hydride and Iron(II) or Iron(III) Chloride for Dehalogenation or Detosylation

7.1.2.10 Method 10: Lithium Aluminum Hydride with Manganese(II) Chloride for the Allylation of Aldehydes or Ketones

7.1.2.11 Method 11: Lithium Aluminum Hydride with Silica Gel for the Reduction of Oxo Esters To Give Hydroxy Esters

7.1.2.12 Method 12: Lithium Aluminum Hydride with Selenium Reagents

7.1.2.12.1 Variation 1: Lithium Aluminum Hydride and Diphenyl Diselenide for Ring Cleavage of Oxetanes and Oxolanes

7.1.2.12.2 Variation 2: Lithium Aluminum Hydride and Elemental Selenium

7.1.2.13 Method 13: Lithium Aluminum Hydride with Vanadium(III) Chloride for Dehalogenative Homocoupling of Benzylic and Allylic Halides

7.1.2.14 Method 14: Lithium Aluminum Hydride with Lithium Iodide for Selective Reduction of β -Alkoxy Ketones

7.1.2.15 Method 15: Lithium Aluminum Hydride with Cerium(III) Chloride for Reductive Dehalogenation and Reduction of Phosphine Oxides to Phosphines

7.1.2.16 Method 16: Lithium Aluminum Hydride with Chromium(III)Chloride

7.1.2.16.1 Variation 1: Lithium Aluminum Hydride with Chromium(III) Chloride for Dehalogenative Reductions

7.1.2.16.2 Variation 2: Lithium Aluminum Hydride with Chromium(III) Chloride in a Grignard-Type Reaction

7.1.2.17 Method 17: Lithium Aluminum Hydride with Alkoxides for the Reduction of Oximes to Amines

7.1.2.18 Method 18: Lithium Aluminum Hydride with Phosphorus Reagents

7.1.2.18.1 Variation 1: Lithium Aluminum Hydride with Diphosphorus Tetraiodide

7.1.2.18.2 Variation 2: Lithium Aluminum Hydride with Hexamethylphosphoric Triamide for the Hydrolysis of Oximes to Ketones

7.1.2.19 Method 19: Amine– and Amide–Aluminate Complexes Prepared from Lithium Aluminum Hydride and Amines

7.1.2.19.1 Variation 1: Preparation of 3-Substituted Pyridines via a Lithium Tetraaminoaluminate Complex Formed from Lithium Aluminum Hydride and Pyridine

7.1.2.19.2 Variation 2: Reduction of Carbonyl Compounds by Lithium Tris(diethylamino)hydroaluminate Prepared from Lithium Aluminum Hydride and Diethylamine

7.1.2.19.3 Variation 3: Ring-Opening Aminations by Lithium Tetraaminoaluminates Prepared from Lithium Aluminum Hydride and Excess Amine

7.1.2.19.4 Variation 4: Lithium Aluminum Hydride–Amine Complexes

7.1.2.20 Method 20: Partial Reduction of Carboxylic Acids and Acid Chlorides to Aldehydes by Sodium Diethyl(hydro)piperidinoaluminate Prepared from Sodium Diethyldihydroaluminate and Piperidine

7.1.2.21 Method 21: Lithium Alkoxyaluminum Hydrides Prepared from Lithium Aluminum Hydride and Alcohols

7.1.2.22 Method 22: Chiral Aluminum Hydrides Formed from Chiral Alcohols or Amines and Lithium or Sodium Aluminum Hydride

7.1.2.23 Method 23: Sodium Tri-tert-butoxy(hydro)aluminate

7.1.2.24 Method 24: Lithium Tri-tert-butoxy(hydro)aluminate

7.1.2.24.1 Variation 1: Asymmetric Reduction of Oxo Groups by Lithium Tri-tert-butoxy(hydro)aluminate

7.1.2.24.2 Variation 2: Use of Lithium Tri-tert-butoxy(hydro)aluminate for the Preparation of Zirconium Complexes

7.1.2.25 Method 25: Sodium Bis(2-methoxyethoxy)aluminum Hydride

7.1.2.26 Method 26: Asymmetric Reduction of Oxo Groups to Hydroxy Groups by Alkoxyaluminum Hydrides

7.1.2.26.1 Variation 1: Asymmetric Reduction of α-Oxo Esters to α-Hydroxy Esters by Lithium Trialkoxy(hydro)aluminates

7.1.2.26.2 Variation 2: Asymmetric Reduction of Ketones to Alcohols by Lithium Trialkoxy(hydro)aluminates

7.1.2.26.3 Variation 3: Asymmetric Reduction of Oxo Groups by Dialkoxyaluminum Hydrides

7.1.2.27 Method 27: Diisobutylaluminum Hydride with Hexamethylphosphoric Triamide

7.1.2.28 Method 28: Diisobutylaluminum Hydride with a Phosphorylacetate

7.1.2.29 Method 29: Diisobutylaluminum Hydride with Triethylamine

7.1.2.30 Method 30: Diisobutylaluminum Hydride with Tin(II) Chloride

7.1.2.31 Method 31: Diisobutylaluminum Hydride with Magnesium(II) Bromide

7.1.2.32 Method 32: Diisobutylaluminum Hydride with Zinc(II) Chloride

7.1.2.33 Method 33: Diisobutylaluminum Hydride with Nickel Compounds

7.1.2.34 Method 34: Diisobutylaluminum Hydride with Boron Trifluoride

7.1.2.35 Method 35: Diisobutylaluminum Hydride with Titanium Compounds

7.1.2.36 Method 36: Diisobutylaluminum Hydride with Lithium Azide

7.1.2.37 Method 37: Diisobutylaluminum Hydride with Alkyllithiums

7.1.2.38 Method 38: Other Stereoselective Synthesis with Diisobutylaluminum Hydride

7.1.2.39 Method 39: Aluminum Trihydride

7.1.2.40 Method 40: Trivalent Aluminum Hydride–Amine and –Amide Complexes from Lithium Aluminum Hydride or Aluminum Trihydride and Amines

7.1.2.41 Method 41: Diaminoaluminum Hydride Complexes from Aluminum(0), Dihydrogen, and Amines

7.1.2.42 Method 42: Trivalent Aluminum Hydride Halides from Lithium Aluminum Hydride and Aluminum Trihalides

7.1.2.43 Method 43: Stereospecific Hydroaluminations of C=C and C≡ C Bonds by Various Aluminum Hydrides

7.1.3 Product Subclass 3: Aluminum Halides

S. Saito

7.1.3 Product Subclass 3: Aluminum Halides

Synthesis of Product Subclass 3

7.1.3.1 Method 1: Aluminum Chloride–Titanium Reagents

7.1.3.2 Method 2: Aluminum Chloride–Zirconium Reagents

7.1.3.3 Method 3: Aminoaluminum Chlorides

7.1.3.4 Method 4: Aluminum Trichloride with Chloroamines

7.1.3.5 Method 5: Ethoxy- and Methoxyaluminum Chlorides

7.1.3.6 Method 6: Aluminum Chlorides with Chiral Alkoxide Ligands

7.1.3.7 Method 7: Aryloxyaluminum Chlorides

7.1.3.8 Method 8: Aluminum Chlorides with Chiral Bialkoxide or Biaryloxide Ligands

7.1.3.9 Method 9: Aluminum Halides with Thiols or Sulfides

7.1.3.10 Method 10: Aluminum Trichloride with Benzeneseleninyl Chloride

7.1.3.11 Method 11: Aluminum Chlorides with Alkylaluminums

7.1.3.12 Method 12: Aluminum Chlorides with Metal Salts

7.1.3.13 Method 13: Aluminum Chloride with an Azidoarene

7.1.3.14 Method 14: Aluminum Trichloride with a Resin

7.1.3.15 Method 15: Aluminum Trichloride without Additives

7.1.3.16 Method 16: Aluminum Fluorides

7.1.3.17 Method 17: Aluminum Triiodide

7.1.4 Product Subclass 4: Aluminum Alkoxides and Phenoxides

T. Ooi and K. Maruoka

7.1.4 Product Subclass 4: Aluminum Alkoxides and Phenoxides

Synthesis of Product Subclass 4

7.1.4.1 Method 1: Reaction of Aluminum with Alcohols

7.1.4.2 Method 2: Treatment of Alkylaluminum Compounds with Alcohols or Phenols

7.1.4.2.1 Variation 1: Dialkylaluminum Carboxylates and Sulfonates

7.1.4.3 Method 3: Treatment of Alkylaluminum Hydrides with Alcohols or Phenols

7.1.4.4 Method 4: Treatment of Lithium Aluminum Hydride with Alcohols or Phenols

Applications of Product Subclass 4 in Organic Synthesis

7.1.4.5 Method 5: Aluminum Alkoxides in Organic Synthesis

7.1.4.5.1 Variation 1: Reduction Reactions

7.1.4.5.2 Variation 2: Oxidation Reactions

7.1.4.5.3 Variation 3: The Tishchenko Reaction

7.1.4.5.4 Variation 4: Alkylation

7.1.4.5.5 Variation 5: The Aldol Reaction

7.1.4.5.6 Variation 6: Michael Addition

7.1.4.5.7 Variation 7: Transformation of Epoxides

7.1.4.6 Method 6: Aluminum Phenoxides in Organic Synthesis

7.1.4.6.1 Variation 1: Carbonyl Addition and Reduction

7.1.4.6.2 Variation 2: Conjugate Addition

7.1.4.6.3 Variation 3: The Aldol Reaction

7.1.4.6.4 Variation 4: The Ene Reaction

7.1.4.6.5 Variation 5: The Pudovik Reaction

7.1.4.6.6 Variation 6: Oxidative Methylation

7.1.4.6.7 Variation 7: α-Alkylationof Carbonyl Compounds

7.1.4.6.8 Variation 8: The Hetero–Diels–Alder Reaction

7.1.4.6.9 Variation 9: The Diels–Alder Reaction

7.1.4.6.10 Variation 10: Cycloaddition

7.1.4.6.11 Variation 11: Discrimination of Ethers

7.1.4.6.12 Variation 12: The Claisen Rearrangement

7.1.4.6.13 Variation 13: Epoxide Rearrangement

7.1.4.6.14 Variation 14: Acetal Cleavage

7.1.4.6.15 Variation 15: Intramolecular Prenyl Transfer Reaction

7.1.4.6.16 Variation 16: Asymmetric Cyclization

7.1.4.6.17 Variation 17: Radical Reactions

7.1.4.6.18 Variation 18: Polymerization

7.1.5 Product Subclass 5: Aluminum Thiolates

T. Ooi and K. Maruoka

7.1.5 Product Subclass 5: Aluminum Thiolates

Synthesis of Product Subclass 5

7.1.5.1 Method 1: Treatment of Alkylaluminum Compounds with Thiols

7.1.5.1.1 Variation 1: Bis(dialkylaluminum) Sulfides

7.1.5.1.2 Variation 2: Bis(diethylaluminum) Sulfate

7.1.5.2 Method 2: Treatment of Aluminum Hydrides with Thiols or Disulfides

Applications of Product Subclass 5 in Organic Synthesis

7.1.5.3 Method 3: Use of Dialkylaluminum Alkanethiolates

7.1.5.3.1 Variation 1: Transformation of Ethers

7.1.5.3.2 Variation 2: Transformation of Epoxides

7.1.5.3.3 Variation 3: Transformation of Acetals

7.1.5.3.4 Variation 4: Transformation of Aldehydes

7.1.5.3.5 Variation 5: Transformation of Esters

7.1.5.3.6 Variation 6: Transformation of α,β -Unsaturated Ketones

7.1.5.3.7 Variation 7: Transformation of α,β -Unsaturated Nitriles

7.1.5.3.8 Variation 8: Transformation of O-Sulfonyloximes

7.1.5.3.9 Variation 9: Transformation of Allyl Phosphate Esters

7.1.5.4 Method 4: Use of Bis(dialkylaluminum) Alkanedithiolates

7.1.5.5 Method 5: Use of Bis(diethylaluminum) Sulfide

7.1.5.6 Method 6: Use of Bis(diethylaluminum) Sulfate

7.1.6 Product Subclass 6: Aluminum Selenolates

T. Ooi and K. Maruoka

7.1.6 Product Subclass 6: Aluminum Selenolates

Synthesis of Product Subclass 6

7.1.6.1 Method 1: Treatment of Alkylaluminum Compounds with Selenium Metal

7.1.6.2 Method 2: Treatment of Aluminum Hydrides with Selenols or Diselenides

7.1.6.3 Method 3: Treatment of Hexamethyldisilaselenane with Dimethylaluminum Chloride or Treatment of Hexabutyldistannaselenane with Trimethylaluminum

Applications of Product Subclass 6 in Organic Synthesis

7.1.6.4 Method 4: Use of Dimethylaluminum Methaneselenolate

7.1.6.5 Method 5: Use of Diisobutylaluminum Benzeneselenolate and Its Derivatives

7.1.6.6 Method 6: Use of Bis(dimethylaluminum) Selenide

7.1.7 Product Subclass 7: Aluminum Amides

T. Ooi and K. Maruoka

7.1.7 Product Subclass 7: Aluminum Amides

Synthesis of Product Subclass 7

7.1.7.1 Method 1: Treatment of Alkylaluminum Compounds with Amines

7.1.7.1.1 Variation 1: Dialkylaluminum Hydrazides

7.1.7.2 Method 2: Treatment of Organoaluminum Hydrides with Amines

7.1.7.2.1 Variation 1: By Reduction of Nitriles

7.1.7.2.2 Variation 2: By Reduction of Azomethines

7.1.7.2.3 Variation 3: By Addition to Enamines

7.1.7.3 Method 3: Treatment of Aluminum Halides with Metal Amides

Applications of Product Subclass 7 in Organic Synthesis

7.1.7.4 Method 4: Transformation of Esters

7.1.7.5 Method 5: Transformation of Lactones

7.1.7.6 Method 6: Transformation of Nitriles

7.1.7.7 Method 7: Transformation of Ketones

7.1.7.8 Method 8: Epoxide Cleavage with Aluminum Reagents

7.1.7.9 Method 9: Isomerization of Epoxides to Allylic Alcohols

7.1.7.10 Method 10: 1, 3-Diene Synthesis

7.1.7.11 Method 11: Transformation of Hydrazones

7.1.7.12 Method 12: N-Alkylation of Allylic Derivatives

7.1.7.13 Method 13: Hydrometalation

7.1.7.14 Method 14: Polymerization

7.1.8 Product Subclass 8: Aluminum Oxide (Alumina)

S. Tsuboi

7.1.8 Product Subclass 8: Aluminum Oxide (Alumina)

Synthesis of Product Subclass 8

7.1.8.1 Method 1: Preparation and Characterization of Aluminum Oxide

Applications of Product Subclass 8 in Organic Synthesis

7.1.8.2 Method 2: Alumina-Promoted Reactions

7.1.8.2.1 Variation 1: Additions and Cyclizations

7.1.8.2.2 Variation 2: Oxidation and Reduction

7.1.8.2.3 Variation 3: Rearrangement and Isomerization

7.1.8.2.4 Variation 4: Elimination and Addition

7.1.8.2.5 Variation 5: Ring Closure and Ring Opening

7.1.8.3 Method 3: Reactions Using Alumina–Potassium Fluoride as a Catalyst

7.1.8.4 Method 4: Reactions Using Alumina–Potassium Hydroxide as a Catalyst

7.1.8.5 Method 5: Synthesis of Halides Using Alumina and a Halogen

7.1.8.6 Method 6: Synthesis of Organic Sulfides Using Alumina and Sodium Sulfide

7.1.8.7 Method 7: Oxidation Using Alumina and Barium or Potassium Manganate

7.1.9 Product Subclass 9: Triorganoaluminum Compounds

M. Oishi

7.1.9 Product Subclass 9: Triorganoaluminum Compounds

Synthesis of Product Subclass 9

7.1.9.1 Method 1: By Reactions of Aluminum Metal with Organic Compounds

7.1.9.1.1 Variation 1: From Alkenes and Hydrogen (Direct Synthesis)

7.1.9.1.2 Variation 2: From Alkyl Halides and Subsequent Disproportionation or Reduction

7.1.9.2 Method 2: By Reaction of Organoaluminum Compounds with Unsaturated Hydrocarbons

7.1.9.2.1 Variation 1: Displacement Reactions

7.1.9.2.2 Variation 2: Alumination of Carbon Brø nsted Acids

7.1.9.3 Method 3: By Reaction with Organometallic Precursors

7.1.9.3.1 Variation 1: From Triorganoborane Compounds

7.1.9.3.2 Variation 2: From Organomercury Compounds

7.1.9.3.3 Variation 3: From Organotin Compounds

7.1.9.3.4 Variation 4: From Grignard and Organolithium Reagents

7.1.9.4 Method 4: From Tetraorganoaluminates

7.1.9.4.1 Variation 1: From Aluminum Halides

7.1.9.4.2 Variation 2: From Active Metals

7.1.9.5 Method 5: By Homologation with Diazoalkanes

Applications of Product Subclass 9 in Organic Synthesis

7.1.9.6 Method 6: Addition to C—C Multiple Bonds

7.1.9.6.1 Variation 1: Carboalumination of Alkenes and Alkynes

7.1.9.6.2 Variation 2: Hydroalumination of Alkenes and Alkynes

7.1.9.6.3 Variation 3: Cyclopropanation

7.1.9.6.4 Variation 4: Conjugate Addition

7.1.9.7 Method 7: Addition Reactions to Carbon—Heteroatom Multiple Bonds

7.1.9.7.1 Variation 1: Reactions with Carbonyl Substrates

7.1.9.7.2 Variation 2: Addition to Imines and Nitriles

7.1.9.8 Method 8: Cleavage and Substitution Reactions of Carbon—Heteroatom Bonds

7.1.9.8.1 Variation 1: Ring Opening of Epoxides and Aziridines

7.1.9.8.2 Variation 2: Cleavage of Acetals and Ketals

7.1.9.8.3 Variation 3: Noncatalyzed Coupling Rections

7.1.9.8.4 Variation 4: Metal-Catalyzed Coupling Reactions

7.1.9.9 Method 9: Rearrangement Reactions

7.1.9.9.1 Variation 1: Claisen Rearrangement

7.1.9.9.2 Variation 2: 1, 3-Rearrangement of Acetals

7.1.9.9.3 Variation 3: 3-Aza-Cope Rearrangement

7.1.9.9.4 Variation 4: Pinacol-Type Rearrangement

7.1.9.9.5 Variation 5: Beckmann-Type Rearrangement

7.1.9.10 Method 10: Polymerization Reactions

7.1.9.10.1 Variation 1: Alkene Polymerization: Chain Transfer, Catalytic, and Cocatalytic Behaviors

7.1.9.10.2 Variation 2: Ionic Polymerization of Polar Monomers

7.1.9.10.3 Variation 3: Radical Polymerization of Polar Monomers

7.1.9.10.4 Variation 4: Ring-Opening Polymerization

7.2 Product Class 2: Gallium Compounds

M. Yamaguchi

7.2 Product Class 2: Gallium Compounds

7.2.1 Product Subclass 1: Organogallium(III) Complexes Containing Gallium—Gallium Bonds

Synthesis of Product Subclass 1

7.2.1.1 Method 1: From Organometallic Compounds and Gallium Halides

7.2.1.2 Method 2: Reductive Coupling of Organogallium(III)Halides

7.2.2 Product Subclass 2: Organogallium(III) Complexes Containing a Bond between Gallium and a Transition Metal

Synthesis of Product Subclass 2

7.2.2.1 Method 1: From Transition Metal Hydrides and Triorganogallium Complexes

7.2.2.2 Method 2: From Transition Metal Anions and Organogallium(III) Halides

7.2.3 Product Subclass 3: Organogallium(III) Halides

Synthesis of Product Subclass 3

7.2.3.1 Method 1: From Organometallic Compounds and Gallium(III) Halides

7.2.3.2 Method 2: Redistribution Reaction between Triorganogallium Complexes and Gallium(III) Halides

7.2.3.3 Method 3: From Alkyl Halides and Gallium(I) Halides

Applications of Product Subclass 3 in Organic Synthesis

7.2.3.4 Method 4: Reactions Involving Organogallium(III) Halides

7.2.4 Product Subclass 4: Organogallium(III) Complexes Containing a Bond between Gallium and a Group 16 Element

Synthesis of Product Subclass 4

7.2.4.1 Method 1: From Triorganogallium Complexes and Chalcogen Elements

7.2.4.2 Method 2: From Organic Acids and Organogallium Complexes

7.2.4.3 Method 3: From Metalated Organic Acids and Gallium(III) Halides

Applications of Product Subclass 4 in Organic Synthesis

7.2.4.4 Method 4: Asymmetric Reactions Employing Gallium Catalysts

7.2.5 Product Subclass 5: Organogallium(III) Complexes Containing a Bond between Gallium and a Group 15 Element

Synthesis of Product Subclass 5

7.2.5.1 Method 1: From Organic Acids and Organogallium Complexes

7.2.5.2 Method 2: From Metalated Organic Acids and Gallium(III) Halides

7.2.6 Product Subclass 6: Triorganogallium(III) Complexes

Synthesis of Product Subclass 6

7.2.6.1 Method 1: From Organometallic Compounds and Gallium(III) Halides

7.2.6.2 Method 2: Redistribution Reaction between Cyclopentadienylgallium(III) Complexes and Trialkylgallium Complexes

Applications of Product Subclass 6 in Organic Synthesis

7.2.6.3 Method 3: Reactions Involving Triorganogallium Complexes

7.2.7 Product Subclass 7: Organogallium(I) Complexes

Synthesis of Product Subclass 7

7.2.7.1 Method 1: From Organometallic Reagents and Gallium(I) Halides

7.2.7.2 Method 2: From Arenes and Gallium(I) Halides

Applications of Product Subclass 7 in Organic Synthesis

7.2.7.3 Method 3: Reductive Coupling Using Gallium(II) Chloride

7.3 Product Class 3: Indium Compounds

T.-P. Loh

7.3 Product Class 3: Indium Compounds

7.3.1 Product Subclass 1: Allylic Indium Complexes

Synthesis of Product Subclass 1

7.3.1.1 Method 1: Addition of Indium Metal to Allylic Halides

7.3.1.1.1 Variation 1: In Dimethylformamide

7.3.1.1.2 Variation 2: In Aqueous Media

7.3.1.1.3 Variation 3: Solvent-Free Conditions

7.3.1.2 Method 2: Insertion of Indium(I) Iodide into Allyl Iodide

7.3.1.3 Method 3: Transmetalation from Allylic Stannanes to Indium(III) Chloride

7.3.1.3.1 Variation 1: In Organic Donor Solvents

7.3.1.3.2 Variation 2: In Aqueous Media

7.3.1.4 Method 4: Diastereoselective Allylation of Carbonyl Compounds

7.3.1.5 Method 5: Enantioselective Allylation of Aldehydes

7.3.1.6 Method 6: Intramolecular Addition

7.3.1.7 Method 7: Carboindation of Alkynes

7.3.1.8 Method 8: Allylation of Enamines and Imines

7.3.1.9 Method 9: Formation of Vinylcyclopropanes from Ketones

7.3.2 Product Subclass 2: Propargylic/Allenylic Indium Complexes

Synthesis of Product Subclass 2

7.3.2.1 Method 1: Addition of Indium Metal to Alkynyl Bromides

7.3.2.1.1 Variation 1: In Dimethylformamide

7.3.2.1.2 Variation 2: In Aqueous Media

7.3.2.1.3 Variation 3: Insertion of Indiumin to Chiral Allenyl Iodides

7.3.2.2 Method 2: Tetrakis(triphenylphosphine)palladium(0)-Catalyzed Insertion of Indium(I) Iodide into 2-Ethynylaziridines

7.3.3 Product Subclass 3: Reformatsky-Type Indium Complexes

Synthesis of Product Subclass 3

7.3.3.1 Method 1: Insertion of Indium Metal into α-Halo Esters and α-Halo Ketones

7.3.3.1.1 Variation 1: In Organic Solvent

7.3.3.1.2 Variation 2: In Aqueous Media

7.3.3.2 Method 2: Insertion of Indium(I) Iodide into α-Iodo Esters

7.3.3.3 Method 3: Enantioselective Aldol-Type Addition

7.3.4 Product Subclass 4: Indium Carbenoids

Synthesis of Product Subclass 4

7.3.4.1 Method 1: Addition of Indium Metal to Activated Dibromomethane —

7.3.5 Product Subclass 5: Alkylindium(III) Complexes

Synthesis of Product Subclass 5

7.3.5.1 Method 1: Addition of Grignard Reagents to Indium(III) Chloride

7.3.5.2 Method 2: Insertion of Indium Metal into an Alkyl Iodide

Applications of Product Subclass 5 in Organic Synthesis

7.3.5.3 Method 3: Cross Coupling with 1-Haloalkenes

7.3.5.4 Method 4: Carboindation of Alkynes with Benzylindium Sesquiiodide

7.3.6 Product Subclass 6: Tetraorganoindates

Synthesis of Product Subclass 6

7.3.6.1 Method 1: Reaction of Triorganoindium Complexes with Alkali Metals

7.3.6.2 Method 2: Reaction of Triorganoindium Complexes with Organolithium Complexes

7.3.6.3 Method 3: Reaction of Triorganoindium Complexes with Organoarsenic or Organoantimony Complexes

Applications of Product Subclass 6 in Organic Synthesis

7.3.6.4 Method 4: 1, 4-Addition to α,β -Unsaturated Carbonyl Compounds

7.3.6.5 Method 5: Allylation of Allylic Bromides

7.3.6.6 Method 6: Addition to Nitriles

7.3.7 Product Subclass 7: Indium(III) Chloride

Synthesis of Product Subclass 7

7.3.7.1 Method 1: From Indium Metal

7.3.7.2 Method 2: From Indium (III) Oxide

Applications of Product Subclass 7 in Organic Synthesis

7.3.7.3 Method 3: Prins-Type Cyclization Reactions

7.3.7.4 Method 4: Michael Addition of Amines

7.3.7.5 Method 5: Direct Aldol Reaction of Glyoxylic Acid

7.3.7.6 Method 6: Mukaiyama Aldol Reaction

7.3.7.7 Method 7: Diels–Alder Reaction

7.3.7.8 Method 8: Imino-Diels–Alder Reaction

7.3.7.9 Method 9: Ionic Diels–Alder Reaction

7.3.7.10 Method 10: One-Pot Mannich-Type Reaction in Water

7.3.7.11 Method 11: Rearrangement of Epoxides

7.3.7.12 Method 12: Epoxide Ring Opening with Aromatic Amines

7.3.7.13 Method 13: Reductive Friedel–Crafts Alkylation

7.3.7.14 Method 14: Deoxygenative Allylation of Aryl Ketones

7.3.7.15 Method 15: Reactions of α-Diazocarbonyl Compounds

7.3.7.16 Method 16: Three-Component Reaction of Alkenes, Glyoxylates, and Amines

7.3.8 Product Subclass 8: Indium(III) Trifluoromethanesulfonate

Applications of Product Subclass 8 in Organic Synthesis

7.3.8.1 Method 1: 2-Oxonia[3, 3]-Sigmatropic Rearrangement-Cyclization

7.3.8.2 Method 2: Acylation of Alcohols and Amines

7.3.8.3 Method 3: Hetero-Diels–Alder Reaction of Danishefsky’s Diene and Imines

7.3.8.4 Method 4: Reusable Catalyst for Intramolecular Diels–Alder Reactions

7.3.8.5 Method 5: [4 + 2] Cycloaddition of Benzopyranone Schiff Bases

7.4 Product Class 4: Thallium Compounds

I. E. Markó

7.4 Product Class 4: Thallium Compounds

7.4.1 Product Subclass 1: Triorganothallium(III) Complexes

Synthesis of Product Subclass 1

7.4.1.1 Method 1: Addition of Organometallic Complexes to Diorganothallium(III) Halides

7.4.1.1.1 Variation 1: Addition of Organolithium Complexes

7.4.1.1.2 Variation 2: Addition of Organomagnesium Compounds

7.4.1.2 Method 2: Addition of Organometallic Complexes to Thallium(III) Salts

7.4.1.3 Method 3: Disproportionation of Thallium(I) Salts

Applications of Product Subclass 1 in Organic Synthesis

7.4.1.4 Method 4: Ketone Synthesis

7.4.1.5 Method 5: Alkylation Reactions

7.4.1.5.1 Variation 1: Stoichiometric Alkylation Reactions

7.4.1.5.2 Variation 2: Catalytic Alkylation Reactions

7.4.2 Product Subclass 2: Tetraorganothallium(III) “Ate” Complexes

Synthesis of Product Subclass 2

7.4.2.1 Method 1: Addition of Organolithium Compounds to Triorganothallium(III) Complexes

7.4.2.2 Method 2: Addition of Organolithium Compounds to Diorganothallium(III) Complexes

Applications of Product Subclass 2 in Organic Synthesis

7.4.2.3 Method 3: Addition to Ketones

7.4.2.4 Method 4: [1, 2] Addition to Enones

7.4.2.5 Method 5: [1, 4] Addition to Enones

7.4.2.6 Method 6: Chemoselective Reactions with Enones

7.4.3 Product Subclass 3: Diorganothallium(III) Complexes

Synthesis of Product Subclass 3

7.4.3.1 Method 1: Addition of Organometallic Complexes to Thallium(III)Salts

7.4.3.2 Method 2: Hydrolysis of Triorganothallium(III) Derivatives

Applications of Product Subclass 3 in Organic Synthesis

7.4.3.3 Method 3: Synthesis of Triorganothallium(III) Derivatives and Their “Ate” Complexes

7.4.3.4 Method 4: Synthetic Utility of Diarylthallium(III)Carboxylates

7.4.4 Product Subclass 4: Monoorganothallium(III) Derivatives

Synthesis of Product Subclass 4

7.4.4.1 Method 1: Addition of Organometallic Complexes to Thallium(III)Salts

7.4.4.2 Method 2: Direct Thallation

Applications of Product Subclass 4 in Organic Synthesis

7.4.4.3 Method 3: Functionalization of Aromatic Complexes

7.4.4.3.1 Variation 1: By Direct Thallation–Iodination

7.4.4.3.2 Variation 2: By Direct Thallation–Thallium Replacement

7.4.4.4 Method 4: Functionalization of Alkenes

7.4.4.5 Method 5: Oxidative Rearrangements

7.4.4.6 Method 6: Oxidation of Alkynes

7.4.4.7 Method 7: α-Hydroxylation of Ketones

7.4.4.8 Method 8: Coupling of Arenes

7.4.4.9 Method 9: Palladium-Catalyzed Reactions

7.4.5 Product Subclass 5: Organothallium(I) Complexes

Synthesis of Product Subclass 5

7.4.5.1 Method 1: Synthesis of Cyclopentadienylthallium(I) by Meister’s Method

Applications of Product Subclass 5 in Organic Synthesis

7.4.5.2 Method 2: Addition to Aliphatic Halides

7.4.5.3 Method 3: Synthesis of Cyclopentadienyl-Containing Organometallic Complexes

7.4.6 Product Subclass 6: Inorganic Thallium(I) Derivatives

Synthesis of Product Subclass 6

7.4.6.1 Method 1: Ligand Exchange

Applications of Product Subclass 6 in Organic Synthesis

7.4.6.2 Method 2: Monoalkylation of β -Dicarbonyl Derivatives

7.4.6.3 Method 3: Additives in Palladium-Catalyzed Reactions

7.5 Product Class 5: Beryllium Compounds

H. Yasuda

7.5 Product Class 5: Beryllium Compounds

7.5.1 Product Subclass 1: Beryllium Hydride Derivatives

Synthesis of Product Subclass 1

7.5.1.1 Method 1: Synthesis of Organoberyllium Hydrides

7.5.1.2 Method 2: Synthesis of Amino- and Alkoxyberyllium Hydrides

7.5.1.3 Method 3: Synthesis of Methylberyllium Borohydride

7.5.2 Product Subclass 2: Beryllium Halide Derivatives

Synthesis of Product Subclass 2

7.5.2.1 Method 1: Reaction of an Alkylberyllium with Halides

7.5.2.2 Method 2: Reaction of Beryllium with Alkyl Halides

7.5.3 Product Subclass 3: Alkoxy(alkyl)beryllium Compounds

Synthesis of Product Subclass 3

7.5.3.1 Method 1: Reaction of an Alkylberyllium Compound with an Alcohol

7.5.4 Product Subclass 4: Alkyl(alkylsulfanyl)beryllium Compounds

Synthesis of Product Subclass 4

7.5.4.1 Method 1: Alkyl(alkylsulfanyl)beryllium Compounds from Thiols

7.5.5 Product Subclass 5: Alkyl(amino)beryllium Compounds

Synthesis of Product Subclass 5

7.5.5.1 Method 1: Reaction of an Alkylberyllium Compound with an Amine

7.5.6 Product Subclasss 6: Diarylberyllium Compounds

Synthesis of Product Subclass 6

7.5.6.1 Method 1: Reaction of Beryllium with Diarylmercury(II) Compounds

7.5.7 Product Subclass 7: Bis(η5-cyclopentadienyl)beryllium and Other Unsaturated Derivatives

Synthesis of Product Subclass 7

7.5.7.1 Method 1: Reaction of Beryllium Halides with Sodium Cyclopentadienide

7.5.7.2 Method 2: Reaction of Beryllium Chloride with Potassium Pentadienide

7.5.8 Product Subclass 8: Dialkylberyllium Compounds

Synthesis of Product Subclass 8

7.5.8.1 Method 1: Reaction of Alkylberyllium Compounds with Dialkylmercury(II) Compounds

7.5.8.2 Method 2: Alkylation of Beryllium Halides

7.5.9 Product Subclass 9: Anionic Beryllium Complexes

Synthesis of Product Subclass 9

7.5.9.1 Method 1: Preparation of Halide or Cyanide Complexes

7.5.9.2 Method 2: Preparation of Alkali Metal Alkyl-and Arylberyllate Compounds

7.5.9.3 Method 3: Preparation of a Hydride Complex

7.6 Product Class 6: Magnesium Compounds

7.6.1 Product Subclass 1: Magnesium Metal

J.-H. Zhang, C. C. K. Keh, and C.-J. Li

7.6.1 Product Subclass 1: Magnesium Metal

Synthesis of Product Subclass 1

7.6.1.1 Method 1: Formation of Rieke Magnesium from Magnesium Halides

Applications of Product Subclass 1in Organic Synthesis

7.6.1.2 Method 2: Magnesium Amalgam for Pinacol Coupling of Carbonyl Compounds

7.6.1.3 Method 3: Magnesium with a Metal Halide as the Reducing Agent

7.6.1.4 Method 4: Magnesium in Methanol for Reduction Reactions

7.6.1.4.1 Variation 1: Selective Reduction of α,β -Unsaturated Compounds

7.6.1.4.2 Variation 2: Reductive Cleavage Reactions

7.6.1.4.3 Variation 3: Other Reductive Applications

7.6.1.5 Method 5: Low-Valent Titanium Reagents from Reduction by Magnesium

7.6.2 Product Subclass 2: Magnesium Hydride

J.-H. Zhang, C. C. K. Keh, and C.-J. Li

7.6.2 Product Subclass 2: Magnesium Hydride

Synthesis of Product Subclass 2

7.6.2.1 Method 1: Formation of Activated Magnesium Hydride

Applications of Product Subclass 2 in Organic Synthesis

7.6.2.2 Method 2: Magnesium Hydride as a Reducing Agent

7.6.2.3 Method 3: Organomagnesium Hydrides as Reducing Agents

7.6.3 Product Subclass 3: Magnesium–Metal Reagents

J.-H. Zhang, C. C. K. Keh, and C.-J. Li

7.6.3 Product Subclass 3: Magnesium–Metal Reagents

Synthesis of Product Subclass 3

7.6.3.1 Method 1: Reaction of Dimethyl(phenyl)silyllithium with Methyl-magnesium Iodide

7.6.3.2 Method 2: Reaction of Tributylstannyllithium with Methylmagnesium Iodide

Applications of Product Subclass 3 in Organic Synthesis

7.6.3.3 Method 3: Metallometalation of Alkyne Derivatives

7.6.4 Product Subclass 4: Alkynyl Grignard Reagents

A. Yanagisawa

7.6.4 Product Subclass 4: Alkynyl Grignard Reagents

Synthesis of Product Subclass 4

7.6.4.1 Method 1: Alkynylmagnesium Halides from Alk-1-ynes and Alkylmagnesium Halides

Applications of Product Subclass 4 in Organic Synthesis

7.6.4.2 Method 2: Displacement Reactions

7.6.4.3 Method 3: Additions to Carbonyl Compounds

7.6.4.4 Method 4: Reactions with Carboxylic Acid Derivatives

7.6.4.5 Method 5: Additions to Aza Aromatics

7.6.5 Product Subclass 5: Aryl Grignard Reagents

A. Yanagisawa

7.6.5 Product Subclass 5: Aryl Grignard Reagents

Synthesis of Product Subclass 5

7.6.5.1 Method 1: Arylmagnesium Halides from Aryl Halides and Magnesium

7.6.5.1.1 Variation 1: From Aryl Halides and Activated Magnesium

Applications of Product Subclass 5 in Organic Synthesis

7.6.5.2 Method 2: Transmetalations with Metal Halides

7.6.5.3 Method 3: Nucleophilic Aromatic Substitutions

7.6.5.4 Method 4: Additions to Carbonyl Compounds

7.6.5.5 Method 5: Reactions with Carboxylic Acid Derivatives

7.6.6 Product Subclass 6: Alkenyl Grignard Reagents

A. Yanagisawa

7.6.6 Product Subclass 6: Alkenyl Grignard Reagents

Synthesis of Product Subclass 6

7.6.6.1 Method 1: Alkenylmagnesium Halides from Alkenyl Halides and Magnesium

7.6.6.1.1 Variation 1: Buta-1, 3-dien-2-ylmagnesium Chloride from 4-Chlorobuta-1, 2-diene and Magnesium

7.6.6.2 Method 2: Hydromagnesiation of Alkynes

7.6.6.3 Method 3: Carbomagnesiation of Alkynes

Applications of Product Subclass 6 in Organic Synthesis

7.6.6.4 Method 4: Displacement Reactions

7.6.6.5 Method 5: Addition to Carbonyl Compounds

7.6.6.6 Method 6: Ring Opening of Epoxides

7.6.7 Product Subclass 7: Propargylic Grignard Reagents

A. Yanagisawa

7.6.7 Product Subclass 7: Propargylic Grignard Reagents

Synthesis of Product Subclass 7

7.6.7.1 Method 1: Propargylmagnesium Halides or Allenylmagnesium Halides from Propargyl Halides, Magnesium, and Mercury(II) Chloride

Applications of Product Subclass 7 in Organic Synthesis

7.6.7.2 Method 2: Displacement Reactions

7.6.7.3 Method 3: Addition to Carbonyl Compounds

7.6.7.3.1 Variation 1: Barbier-Type Propargylation of Aldehydes

7.6.7.4 Method 4: Ring Opening of Epoxides

7.6.7.5 Method 5: Additions to Aza Aromatics

7.6.8 Product Subclass 8: Benzylic Grignard Reagents

A. Yanagisawa

7.6.8 Product Subclass 8: Benzylic Grignard Reagents

Synthesis of Product Subclass 8

7.6.8.1 Method 1: Benzylmagnesium Halides from Benzyl Halides and Magnesium

7.6.8.1.1 Variation 1: From Benzyl Halides and Activated Magnesium

Applications of Product Subclass 8 in Organic Synthesis

7.6.8.2 Method 2: Displacement Reactions with Alkyl Halides

7.6.8.3 Method 3: Ring Opening of Epoxides and Oxetane

7.6.8.4 Method 4: Additions to Imines

7.6.8.5 Method 5: Additions to Nitriles

7.6.8.6 Method 6: Additions to Nitro Compounds

7.6.9 Product Subclass 9: Allylic Grignard Reagents

A. Yanagisawa

7.6.9 Product Subclass 9: Allylic Grignard Reagents

Synthesis of Product Subclass 9

7.6.9.1 Method 1: Allylic Magnesium Halides from Allylic Halides and Magnesium

7.6.9.1.1 Variation 1: From Allylic Halides and Activated Magnesium

7.6.9.2 Method 2: Hydromagnesiation of Conjugated Dienes

Applications of Product Subclass 9 in Organic Synthesis

7.6.9.3 Method 3: Displacement Reactions with Alkyl Halides

7.6.9.3.1 Variation 1: Displacement Reactions with Allylic Phosphates

7.6.9.3.2 Variation 2: Transmetalations with Metal Halides Including Chlorosilanes

7.6.9.4 Method 4: Addition to Carbonyl Compounds

7.6.9.4.1 Variation 1: Barbier-Type Allylation of Aldehydes

7.6.9.5 Method 5: Reactions with Carboxylic Acid Derivatives

7.6.9.6 Method 6: Addition to Imines

7.6.9.6.1 Variation 1: Addition to Nitriles

7.6.9.6.2 Variation 2: Addition to Aza Aromatics

7.6.9.7 Method 7: Addition to Nitro Compounds

7.6.9.8 Method 8: Addition to Alkenes

7.6.9.8.1 Variation 1: Addition to Conjugated Dienes

7.6.10 Product Subclass 10: Alkyl Grignard Reagents

K. Oshima

7.6.10 Product Subclass 10: Alkyl Grignard Reagents 573

Synthesis of Product Subclass 10

7.6.10.1 Method 1: Reaction of Simple Alkyl Halides with Magnesium

7.6.10.1.1 Variation 1: Synthesis of Methylmagnesium Halides

7.6.10.1.2 Variation 2: Synthesis of Ethyl- and Butylmagnesium Halides

7.6.10.1.3 Variation 3: Synthesis of Isopropyl-, sec-Butyl-, and Cyclopropyl-magnesium Halides

7.6.10.1.4 Variation 4: Synthesis of Isobutylmagnesium Halides

7.6.10.1.5 Variation 5: Synthesis of tert-Butylmagnesium Halides

7.6.10.1.6 Variation 6: Synthesis of Dialkylmagnesium Compounds

7.6.10.2 Method 2: Reaction of Dihaloalkanes with Magnesium

7.6.10.3 Method 3: Reaction of 1-Haloalk-3-enes, 1-Haloalk-4-enes, or Their Cyclopropyl Synthetic Equivalents with Magnesium

7.6.10.4 Method 4: Reaction of 1-Haloalk-3-ynes or Their Cyclopropyl Synthetic Equivalents with Magnesium

7.6.10.5 Method 5: Reaction of Alkoxyalkyl Halides or Their Analogues with Magnesium

7.6.10.6 Method 6: Reaction of (Trimethylsilyl)methyl Halides with Magnesium

7.6.10.7 Method 7: Reaction of Alkyllithium Compounds with Magnesium Halides

Applications of Product Subclass 10 in Organic Synthesis

7.6.10.8 Method 8: Addition to Carbonyl Compounds

7.6.10.8.1 Variation 1: Synthesis of Alcohols: Addition of Alkyl Groups to Carbonyl Moieties

7.6.10.8.2 Variation 2: Reduction of Hindered Ketones

7.6.10.8.3 Variation 3: Addition of [(Trimethylsilyl)methyl]magnesium Chloride or [(Isopropoxydimethylsilyl)methyl]magnesium Chloride

7.6.11 Product Subclass 11: Grignard Reagents with Transition Metals

T. Takahashi and Y. Liu

7.6.11 Product Subclass 11: Grignard Reagents with Transition Metals

Synthesis of Product Subclass 11

7.6.11.1 Method 1: Grignard Reagents with Catalytic Dichlorobis(phosphine)nickel(II)

7.6.11.2 Method 2: Coupling Reactions Using Nickel–Phosphine Catalysts

7.6.11.2.1 Variation 1: Nickel-Catalyzed Coupling of Grignard Reagents with Alkyl Compounds

7.6.11.2.2 Variation 2: Nickel-Catalyzed Coupling of Grignard Reagents with Allyl Compounds

7.6.11.2.3 Variation 3: Nickel-Catalyzed Enantioselective Coupling of Grignard Reagents with Allyl Compounds

7.6.11.2.4 Variation 4: Nickel-Catalyzed Coupling of Grignard Reagents with Vinyl or Aryl Compounds

7.6.11.2.5 Variation 5: Nickel-Catalyzed Enantioselective Coupling of Grignard Reagents with Aryl Compounds

7.6.11.3 Method 3: Coupling Reactions Using Catalytic Bis(acetyl-acetonato)nickel(II) or Nickel(II) Chloride

7.6.11.4 Method 4: Coupling Reactions Using Catalytic Nickel(II) Chloride and Buta-1, 3-diene

7.6.11.5 Method 5: Grignard Reagents with Catalytic Dichlorobis(phosphine)palladium(II)

7.6.11.6 Method 6: Coupling Reactions Using Palladium Catalysts

7.6.11.6.1 Variation 1: Palladium-Catalyzed Coupling Reactions of Grignard Reagents with Allyl Compounds

7.6.11.6.2 Variation 2: Palladium-Catalyzed Coupling of Grignard Reagents with Vinyl or Aryl Compounds

7.6.11.6.3 Variation 3: Palladium-Catalyzed Enantioselective Coupling of Grignard Reagents

7.6.11.7 Method 7: Ethylmagnesium Bromide with Catalytic Titanium(IV) Isopropoxide

7.6.11.7.1 Variation 1: Reaction of Titanacyclopropane

7.6.11.7.2 Variation 2: Alkylmagnesium Bromide with Catalytic Titanium(IV) Isopropoxide

7.6.11.8 Method 8: Titanacyclopropane and Titanacyclopropene Formation by p-Ligand Exchange

7.6.11.9 Method 9: Isopropylmagnesium Bromide (or Isobutylmagnesium Bromide) with Catalytic Dichlorobis(η5-cyclopentadienyl)titanium(IV)

7.6.11.10 Method 10: Butylmagnesium Chloride with Catalytic Dichlorobis(η5-cyclopentadienyl)titanium(IV)

7.6.11.11 Method 11: Cyclopropanation

7.6.11.11.1 Variation 1: Enantioselective Formation of Cyclopropanol

7.6.11.11.2 Variation 2: Intramolecular Formation of a Cyclopropanol

7.6.11.11.3 Variation 3: Formation of Cyclopropylamine

7.6.11.12 Method 12: Reduction

7.6.11.12.1 Variation 1: Reduction of Carbon—Heteroatom Double Bonds

7.6.11.12.2 Variation 2: Reduction of Aryl and Vinyl Halides

7.6.11.13 Method 13: Hydromagnesiation of Unsaturated C—C Bonds

7.6.11.14 Method 14: Carbomagnesiation

7.6.11.15 Method 15: Ethylmagnesium Halide with Catalytic Dichlorobis(η5-cyclopentadienyl)zirconium(IV)

7.6.11.15.1 Variation 1: Formation of a Zirconium–Ethene Complex

7.6.11.15.2 Variation 2: Catalytic Reactions of the Zirconium–Ethene Complex

7.6.11.16 Method 16: Butylmagnesium Halides with Catalytic Dichlorobis(η5-cyclopentadienyl)zirconium(IV)

7.6.11.17 Method 17: Catalytic Reactions Using the Zirconium-Ethene Complex

7.6.11.17.1 Variation 1: Ethylmagnesiation of Alkenes (Dzhemilev Reaction)

7.6.11.17.2 Variation 2: Enantioselective Ethylmagnesiation of Alkenes

7.6.11.17.3 Variation 3: Ethylmagnesiation of Alkynes

7.6.11.17.4 Variation 4: Ethylation of Allylic Ethers

7.6.11.17.5 Variation 5: Enantioselective Ethylation of Allylic Ethers

7.6.11.17.6 Variation 6: Cyclobutene Formation

7.6.11.18 Method 18: Reaction of the Zirconium–Butene Complex

7.6.11.18.1 Variation 1: Cyclomagnesiation of Dienes

7.6.11.18.2 Variation 2: Enantioselective Cyclomagnesiation of Dienes

7.6.11.18.3 Variation 3: Cycloallylation

7.6.11.18.4 Variation 4: Alkylation of Styrene

7.6.11.19 Method 19: Grignard Reagents with Iron Compounds

7.6.11.20 Method 20: Grignard Reagents with Manganese Compounds

7.6.12 Product Subclass 12: Magnesium Halides

M. Shimizu

7.6.12 Product Subclass 12: Magnesium Halides

Synthesis of Product Subclass 12

7.6.12.1 Method 1: Synthesis of Magnesium Fluoride

7.6.12.2 Method 2: Synthesis of Magnesium Chloride

7.6.12.3 Method 3: Synthesis of Magnesium Bromide–Diethyl Ether Complex

7.6.12.4 Method 4: Synthesis of Magnesium Bromide–Tetrahydrofuran Complex

7.6.12.5 Method 5: Synthesis of Magnesium Iodide–Diethyl Ether Complex and Magnesium Iodide

Applications of Product Subclass 12 in Organic Synthesis

7.6.12.6 Method 6: Reactions Involving Magnesium Fluoride

7.6.12.7 Method 7: Reactions Involving Magnesium Chloride as a Lewis Acid

7.6.12.8 Method 8: Reactions Involving Magnesium Chloride–Sodium Iodide

7.6.12.9 Method 9: Reactions Involving Magnesium Bromide as a Lewis Acid

7.6.12.9.1 Variation 1: Magnesium Bromide Promoted Addition to Aldehydes

7.6.12.9.2 Variation 2: Rearrangement of Epoxides Using Magnesium Bromide

7.6.12.10 Method 10: Bromination Reactions Involving Magnesium Bromide

7.6.12.11 Method 11: Reactions Promoted by Magnesium Iodide

7.6.12.11.1 Variation 1: Rearrangement of Epoxides with Magnesium Iodide

7.6.12.11.2 Variation 2: Other Regioselective Reactions Promoted by Magnesium Iodide

7.6.12.12 Method 12: Iodination Reactions Involving Magnesium Iodide

7.6.13 Product Subclass 13: Magnesium Oxide, Alkoxides, and Carboxylates

M. Shimizu

7.6.13 Product Subclass 13: Magnesium Oxide, Alkoxides, and Carboxylates

Synthesis of Product Subclass 13

7.6.13.1 Method 1: Synthesis of Magnesium Oxide

7.6.13.2 Method 2: Synthesis of Magnesium Methoxide

7.6.13.3 Method 3: Synthesis of Magnesium 2-Ethoxyethoxide

7.6.13.4 Method 4: Synthesis of Diethyl (Ethoxymagnesio)malonate

7.6.13.5 Method 5: Synthesis of Methylmagnesium Carbonate

7.6.13.6 Method 6: Synthesis of Magnesium Ethyl Malonate

7.6.13.7 Method 7: Synthesis of Magnesium Monoperoxyphthalate Hexahydrate

7.6.13.8 Method 8: Synthesis of Other Magnesium Carboxylates

Applications of Product Subclass 13 in Organic Synthesis

7.6.13.9 Method 9: Reactions Involving Magnesium Oxide

7.6.13.10 Method 10: Reactions Involving Magnesium Methoxide

7.6.13.11 Method 11: Reactions Involving Magnesium 2-Ethoxyethoxide

7.6.13.12 Method 12: Reactions Involving Diethyl (Ethoxymagnesio)malonate

7.6.13.13 Method 13: Reactions Involving Methylmagnesium Carbonate

7.6.13.14 Method 14: Reactions Involving Magnesium Ethyl Malonate

7.6.13.15 Method 15: Oxidations by Magnesium Monoperoxyphthalate Hexahydrate

7.6.13.16 Method 16: Reactions Involving Other Magnesium Carboxylates

7.6.14 Product Subclass 14: Magnesium Amides

M. Shimizu

7.6.14 Product Subclass 14: Magnesium Amides

Synthesis of Product Subclass 14

7.6.14.1 Method 1: Synthesis of Methylmagnesium N-Cyclohexyl-N-isopropylamide

7.6.14.2 Method 2: Synthesis of Magnesium Bis(diisopropylamide)

7.6.14.3 Method 3: Synthesis of Magnesium Bis(2, 2, 6, 6-tetramethylpiperidide)

7.6.14.4 Method 4: Synthesis of Other Magnesium Bis(dialkylamides)

Applications of Product Subclass 14 in Organic Synthesis

7.6.14.5 Method 5: Reactions Involving Methylmagnesium N-Cyclohexyl-N-isopropylamide

7.6.14.6 Method 6: Reactions Involving Magnesium Bis(diisopropylamide)

7.6.14.7 Method 7: Reactions Involving Magnesium Bis(2, 2, 6, 6-tetramethylpiperidide)

7.6.14.8 Method 8: Reactions Involving Magnesium Bis(dialkylamides)

7.6.15 Product Subclass 15: Dialkyl- and Diarylmagnesiums

J.-H. Zhang, C. C. K. Keh, and C.-J. Li

7.6.15 Product Subclass 15: Dialkyl-and Diarylmagnesiums

Synthesis of Product Subclass 15

7.6.15.1 Method 1: Preparation from Grignard Reagents

7.6.15.1.1 Variation 1: Reaction of Grignard Reagents with Organolithium Compounds

7.6.15.2 Method 2: Reaction of Diorganomercury(II) Compounds with Magnesium

7.6.15.3 Method 3: Reaction of Hydrocarbons with Magnesium

Applications of Product Subclass 15 in Organic Synthesis

7.6.15.4 Method 4: Asymmetric Addition of Dialkylmagnesium to Aldehydes

7.6.15.5 Method 5: Application of Magnesium–Diene Reagents in Organic Synthesis

7.7 Product Class 7: Calcium Compounds

K. Mochida

7.7 Product Class 7: Calcium Compounds

7.7.1 Product Subclass 1: Organocalcium Hydrides

Synthesis of Product Subclass 1

7.7.1.1 Method 1: By Direct Reaction

7.7.2 Product Subclass 2: Organocalcium Halides

Synthesis of Product Subclass 2

7.7.2.1 Method 1: By Direct Reactions

7.7.2.2 Method 2: By Indirect Reactions

7.7.3 Product Subclass 3: Diorganocalcium Compounds

Synthesis of Product Subclass 3

7.7.3.1 Method 1: By Transmetalation and Direct Reactions

7.8 Product Class 8: Strontium Compounds

N. Miyoshi

7.8 Product Class 8: Strontium Compounds

7.8.1 Product Subclass 1: Alkylstrontium Halides

Synthesis of Product Subclass 1

7.8.1.1 Method 1: From Alkyl Halides and Strontium Metal or Activated Strontium

Applications of Product Subclass 1 in Organic Synthesis

7.8.1.2 Method 2: Reaction of Carbonyl Compounds with Alkylstrontium Halides

7.8.1.3 Method 3: Reaction of Vinylacetylenes with Alkylstrontium Halides

7.8.1.4 Method 4: Reactions with Allylic Strontium Reagents

7.8.2 Product Subclass 2: Dialkylstrontium

Synthesis of Product Subclass 2

7.8.2.1 Method 1: From Dialkylzincand Strontium Metal

Applications of Product Subclass 2 in Organic Synthesis

7.8.2.2 Method 2: Reaction of Vinylacetylenes with Dialkylstrontium

7.8.3 Product Subclass 3: Metallocyclic Compounds of Strontium

Synthesis of Product Subclass 3

7.8.3.1 Method 1: From 1, 3-Dienes and Activated Strontium

Applications of Product Subclass 3 in Organic Synthesis

7.8.3.2 Method 2: Reaction of Dichloroalkanes with Metallocyclic Compounds of Strontium

7.8.4 Product Subclass 4: Strontium Metallocenes and Related Compounds

Synthesis of Product Subclass 4

7.8.4.1 Method 1: From Cyclopentadiene and Strontium Metal or Strontium Halide

7.8.5 Product Subclass 5: Miscellaneous Compounds of Strontium

Synthesis of Product Subclass 5

7.8.5.1 Method 1: Synthesis in Ammonia-Saturated Ethereal Solvents

7.9 Product Class 9: Barium Compounds

A. Yanagisawa

7.9 Product Class 9: Barium Compounds

7.9.1 Product Subclass 1: Barium

Synthesis of Product Subclass 1

7.9.1.1 Method 1: Activated Barium from Barium Iodide and Lithium Biphenylide

Applications of Product Subclass 1 in Organic Synthesis

7.9.1.2 Method 2: Homocoupling of Allylic Halides

7.9.1.2.1 Variation 1: Cross Coupling of Allylic Halides with Allylic Phosphates

7.9.1.3 Method 3: Reactions of Conjugated Dienes with Dichloroalkanes

7.9.2 Product Subclass 2: Barium–Metal Reagents

Synthesis of Product Subclass 2

7.9.2.1 Method 1: Barium Ferrate(VI) Monohydrate from Sodium Ferrate and Barium Nitrate

7.9.2.2 Method 2: Barium Dihydroxytrioxoruthenate(VI) from Ruthenium(III) Chloride and Barium Nitrate

7.9.2.3 Method 3: Barium Manganate from Potassium Permanganate or Potassium Manganate and Barium Chloride

Applications of Product Subclass 2 in Organic Synthesis

7.9.2.4 Method 4: Oxidation of Alcohols to Aldehydes and Ketones

7.9.2.4.1 Variation 1: Oxidation of Aromatic Aldehydes to Aromatic Acids

7.9.2.5 Method 5: Oxidation of Diols to Lactones

7.9.2.6 Method 6: Oxidative Coupling of Thiols to Disulfides

7.9.2.7 Method 7: Azo Compounds by Oxidative Coupling of Aromatic Amines

7.9.2.8 Method 8: Oxidation of Alkanes to Carbonyl Compounds

7.9.2.9 Method 9: Dehydrogenation of 4, 5-Dihydroimidazoles

7.9.3 Product Subclass 3: Barium Hydroxide

Applications of Product Subclass 3 in Organic Synthesis

7.9.3.1 Method 1: Partial Hydrolysis of Diesters

7.9.3.2 Method 2: Decarboxylations of Dicarboxylic Acid Derivatives

7.9.3.2.1 Variation 1: Deacylation of β -Oxo Carbonyl Compounds

7.9.3.3 Method 3: Favorskii-Type Ring Contraction of α-Chloro-δ-lactams

7.9.3.4 Method 4: Horner–Wadsworth–Emmons Reactions

7.9.3.5 Method 5: Suzuki Coupling of Sterically Hindered Arylboronic Acids with Aryl Halides

7.9.4 Product Subclass 4: Allylic Barium Reagents

Synthesis of Product Subclass 4

7.9.4.1 Method 1: From Allyllithiums and Barium Iodide

7.9.4.2 Method 2: From Allylic Halides and Activated Barium

Applications of Product Subclass 4 in Organic Synthesis

7.9.4.3 Method 3: Cross-Coupling Reactions with Allylic Halides

7.9.4.3.1 Variation 1: With Allylic Phosphates

7.9.4.3.2 Variation 2: Silylation of Allylic Barium Reagents

7.9.4.3.3 Variation 3: Reactions of Siloxyallylbarium Reagents with Alkyl Halides

7.9.4.4 Method 4: Additions to Carbonyl Compounds

7.9.4.4.1 Variation 1: Additions to Carbonyl Compounds in the Presence of Crown Ethers

7.9.4.4.2 Variation 2: Addition to a Carbonyl Compound in the Presence of a Borane

7.9.4.4.3 Variation 3: Addition to Carbon Dioxide

7.9.4.4.4 Variation 4: Additions of Siloxyallylbarium Reagents to Carbonyl Compounds

7.9.4.5 Method 5: Conjugate Additionsto Enones

7.9.4.6 Method 6: Ring Opening of Epoxides

7.9.4.7 Method 7: Additions to Imines

Keyword Index

Author Index

Abbreviations

Introduction

H. Yamamoto

This volume describes the organometallic, metalloorganic, and organic chemistry of the elements in groups 13 and 2, namely aluminum, gallium, indium, thallium, beryllium, magnesium, calcium, strontium, and barium. Boron is not included here as its compounds will be discussed in an independent volume [Science of Synthesis, Vol. 6(Boron Compounds)]. The objective of this volume is to detail reliable synthetic procedures for compounds of the elements of groups 13 and 2 already known to be valuable synthetic intermediates or subjects of current research work. The breadth of chemistry displayed here is remarkable and, as is characteristic of the series, each author is an expert in their particular field of chemistry and provides a truly selective and critical evaluation of recent and previous developments. Emphasis has been placed on the applications of the compounds synthesized and, wherever appropriate, reliable experimental procedures are described in the text.

Generally, the organization of the sections follows the rules used throughout the series. However, some metalloorganic and inorganic compounds, such as aluminum aryloxides and aluminum oxide (alumina) (Sections 7.1.4 and 7.1.8, respectively), are included in the text.

Aluminum, the most abundant metal in the lithosphere, is widely used either as the metal itself, or is present in numerous compounds that are important in daily life and represent valuable tools for chemists, e.g. alkylaluminum derivatives and aluminum aryloxides and amides. Recent results of organic syntheses involving various aluminum catalysts are also included in this volume, such as the conjugate addition of a nucleophile to benzaldehyde or benzoyl chloride using aluminum tris(2, 6-diphenylphenoxide) (ATPH, 1) as catalyst (Scheme 1).[1,2]

▶ Scheme 1 Conjugate Addition to Benzaldehyde or Benzoyl Chloride Using an Aluminum Catalyst[1,2]

Gallium and indium have attained considerable importance in material science; their compounds are discussed in Sections 7.2 and 7.3, respectively. Section 7.4 deals with thallium. Due to their transmission of long-wavelength light, thallium halides have become highly useful in several special infrared techniques. Aqueous solutions of thallium esters have also been used for small-scale mineral separation because of their high density. The unique chemical and physical properties of all these metals are still very interesting not only for material science, but also for the design of catalysts. For example, gallium sodium bis(1, 1′-bi-2-naphthoxide) (2) has been found to be an excellent catalyst for the asymmetric Michael addition of malonates to cycloalk-2-enones, such as in the formation of 3 (Scheme 2).[3]

▶ Scheme 2 Asymmetric Michael Addition of a Malonate to Cyclohex-2-enone Using a Gallium Catalyst[3]

Among the organometallic compounds of group 2, organomagnesium compounds (Section 7.6) are of prime importance because of their manifold applications in preparative chemistry. Therefore, they are discussed in great detail in comparison to those compounds of calcium and heavier alkali earth metals. Over 100 years have passed since Grignard published his historic paper on the preparation of ethereal solutions of compounds in which carbon is directly bonded to magnesium.[4] Even now, Grignard reagents are an obvious choice for organic chemists in many molecule preparations. Although the wide range of applications of the Grignard reagent is truly impressive, the actual mechanistic details of this well-known organometallic compound are still vague. We have had to wait for recent advances in various analytical techniques to understand, even partly, the true details of reactions using this classical reagent. Now that its various mechanisms are understood, the role of the Grignard reagent in organic synthesis is recognized to be even greater than previously anticipated. Accordingly, magnesium is used far more in preparative chemistry, and its compounds are described in detail in this volume.

In contrast, the heavier elements form bonds with a more pronounced ionic character, providing unique synthetic opportunities. Barium compounds, for example, show contrasting regioselectivity to the magnesium derivatives (Scheme 3).[5]

▶ Scheme 3 Regioselectivity of the Carboxylation Reactions of Organobarium and Organomagnesium Compounds[5]

It should also be emphasized that the reagents mentioned here are both useful and safer than most of the transition-metal compounds. This is an advantageous feature of compounds of the main group of elements with respect to the issue of green chemistry.

References

[1] Maruoka, K.; Ito, M.; Yamamoto, H., J. Am. Chem. Soc., (1995) 117, 9091.

[2] Saito, S.; Sone, T.; Murase, M.; Yamamoto, H., J. Am. Chem. Soc., (2000) 122, 10216.

[3] Shibasaki, M.; Sasai, H.; Arai, T., Angew. Chem., (1997) 109, 1290; Angew. Chem. Int. Ed. Engl., (1997) 36, 1237.

[4] Grignard, V., C. R. Hebd. Seances Acad. Sci., (1900) 130, 1322.

[5] Yanagisawa, A.; Yasue, K.; Yamamoto, H., Org. Synth., Coll. Vol. IX, (1998), 317.

7.1 Product Class 1: Aluminum Compounds

7.1.1 Product Subclass 1: Zerovalent Aluminum and Its Alloys

S. Saito

General Introduction

Aluminum(0) is a typical one-electron-transfer agent, with a low first ionization potential of 5.986 eV, to give aluminum(III); this makes it one of the most reducing metals. This characteristic advantage is well featured, for example, not only in the reduction of several transition metals and organic molecules, but also in pinacol- or McMurry-type coupling. In addition, aluminum has the advantage of being readily available, inexpensive, stable, easy to handle, nontoxic, and resistant to water because it forms a thin film of insoluble alumina that protects against further reaction.

Synthesis of Product Subclass 1

7.1.1.1 Method 1: Aluminum Treated with Mercury(II) Chloride

Reduction of mercury(II) chloride to mercury(0) with excess aluminum(0) gives aluminum amalgam,[1–5] which is a very useful reducing agent for many functional groups.[6] For example, sulfinyl and phosphorus ylide groups can be reduced by this reagent, presumably by electron transfer from mercury(0), and subsequent protonation gives the corresponding hydrocarbons. Aluminum amalgam is also used for the selective removal of sulfinyl and phosphorus ylide groups from ketones, for example, the conversion of methylsulfinyl ketone 1 into acetophenone (2) (▶ Scheme 1).[5] Aluminum amalgam is a shiny solid, which has been prepared by many different methods, and which generally reacts vigorously with water with liberation of hydrogen gas equivalent to the amount of aluminum present. It is therefore also used to dry organic solvents (e.g., diethyl ether, ethanol). It can be stored under dry diethyl ether.

▶ Scheme 1 Selective Removal of Sulfinyl and Phosphorus Ylide Groups from Ketones with Aluminum Amalgam[5]

Aluminum Amalgam:[1,2]

CAUTION:

Mercury(II) chloride is a poison by ingestion and is toxic by skin contact. When heated to decomposition it emits toxic fumes of mercury.

Al turnings (oil-free) were etched with dil NaOH to the point of rapid H2 evolution; the soln was then decanted, and the metal was superficially washed once with H2O so that some alkali was left behind. It was then treated with 0.5% aq HgCl2 for 1–2 min, and the entire process was repeated. The shiny amalgamated metal was washed rapidly in turn with H2O, EtOH, and Et2O and was used at once. This material reacted vigorously with H2O with liberation of H2 equivalent to the amount of Al present and could be used to dry Et2O or EtOH.

Aluminum Amalgam:[3]

CAUTION:

Mercury(II) chloride is a poison by ingestion and is toxic by skin contact. When heated to decomposition it emits toxic fumes of mercury.

A 25-mL flask was charged with Al chips (5 mm × 5 mm) cut from Al foil (360 mg, 13.3 mmol). A 2% aq soln of HgCl2 (15 mL) was added, the mixture was stirred by hand for 1 min, and then the aqueous phase was removed by a water-vacuum-aspirated pipet. The chips were washed successively with abs EtOH (5 × 20 mL), anhyd Et2O (5 × 15 mL), and dry THF (5 × 15 mL); the washings were removed each time by decantation. Fresh THF (20 mL) was added, and the mixture was ready for use in further reactions.

Aluminum Trimethoxide Solution in Methanol:[4]

CAUTION:

Mercury(II) chloride is a poison by ingestion and is toxic by skin contact. When heated to decomposition it emits toxic fumes of mercury.

A mixture of Al foil (2.70 g, 100 mmol), HgCl2 (51 mg, 0.19 mmol), and dry MeOH (50 mL) was refluxed until all the Al had dissolved to give a gray suspension. CCl4 (1 mL) (CAUTION:toxic), which acts as a catalyst, was added to the boiling mixture. After the mixture had cooled to rt, dry MeOH was added to adjust the volume of the soln to 100 mL, to give a 1M soln of Al(OMe)3 in MeOH.

Acetophenone (2);Typical Procedure:[5]

CAUTION:

Mercury(II) chloride is a poison by ingestion and is toxic by skin contact. When heated to decomposition it emits toxic fumes of mercury.

To prepare the Al/Hg amalgam, Al foil was cut into strips of approximately 10 cm × 1.0 cm, and these were immersed, all at once, into a 2% aq soln of HgCl2 for 15 s. After the strips had been rinsed with abs EtOH followed by Et2O, they were cut into 1.0 cm × 1.0 cm squares, directly into the reaction vessel. A mixture of methylsulfinyl ketone 1 (0.5 g, 2.75 mmol), the Al/Hg amalgam (28 mg), and aq THF (30 mL) was stirred at 0°C for 10 min. The mixture was then filtered, and the filtered solids were washed with THF. The filtrate was concentrated to remove most of the THF, Et2O was added, and the Et2O phase was separated from the aqueous phase. The Et2O soln was dried (Na2SO4) and concentrated; this left behind pure acetophenone (2); yield: 98%.

7.1.1.2 Method 2: Aluminum Treated with Potassium Hydroxide in Methanol

There are several methods in which aluminum(0) is used under strongly basic conditions in an alcoholic solvent. Typically, aromatic ketones, e.g. acetophenone, undergo pinacol coupling in the presence of aluminum powder, potassium hydroxide, and methanol (▶ Scheme 2).[5] A novel, rapid, one-pot procedure for the reductive coupling of aldimines (e.g., 3) has been described, in which the inexpensive reagents aluminum powder and potassium hydroxide are used (▶ Scheme 2).[7,8] The vicinal diamines (e.g., 4) are generally obtained in excellent yields without the formation of side products. However, the rac selectivity is consistently found to be only moderate [(rac/meso) 60:40 to 85:15].

▶ Scheme 2 Pinacol Coupling of an Aromatic Ketone or Imine Promoted by Aluminum with Potassium Hydroxide[5,7,8]

N,N′, 1, 2-tetraphenylethane-1, 2-diamine (4);Typical Procedure:[7,8]

Benzylideneaniline (3; 1.8 g, 10 mmol) was dissolved in MeOH (10 mL). Al powder (0.27 g, 10 mmol) and KOH (1.7 g, 30 mmol) were added, and the mixture was stirred at rt. The reaction became vigorous immediately after the addition of KOH. After 10 min, the mixture was filtered to remove the Al powder, and H2O (40 mL) was added to the filtrate. The filtrate was then extracted with CHCl3 (3 × 20 mL), and the soln was dried (Na2SO4) and concentrated under reduced pressure; N,N′, 1, 2-tetraphenylethane-1, 2-diamine (4) was obtained as a mixture of diastereomers [(rac/meso) 7:3]; yield: 90%.

7.1.1.3 Method 3: Aluminum as Reductant for Titanium(IV) Chloride

Aluminum metal is a good reducing agent for titanium(IV) chloride, and attempts to use a catalytic amount of low-valent titanium have proved successful. In combination with aluminum metal, titanium can be used catalytically to effect Barbier-type allylation of imines (▶ Scheme 3).[9] In the absence of titanium(IV) chloride, the reaction does not occur at all. The aluminum(III) salts that accumulate in the medium function as a Lewis acid to form iminium ions, which, in turn, undergo allylation, leading to homoallylamines, e.g. 5. The course of the reaction depends considerably on the titanium/aluminum ratio. For example, titanium/aluminum ratios of 3:1 and 3:2 (to 1 equivaldimine), formally corresponding to one- and two-electron reductions, provide suspensions of different colors: green [possibly due to Ti(III)] and blue [possibly due to Ti(II)]. Neither of the reagents on its own give coupling products, whereas titanium/aluminum ratios of 1:1 and 3:4 result in yields of 29 and 38%, respectively. The benzaldimine derived from L-valine undergoes an asymmetric version of this process.

▶ Scheme 3 Allylation of an Imine Catalyzed by a Low-Valent Titanium Reagent Generated from Titanium(IV) by Reduction by Aluminum[9]

Benzyl(1-phenylbut-3-enyl)amine (5);Typical Procedure:[9]

Into a mixture of N-benzylbenzylideneamine (0.195 g, 1 mmol) and finely cut Al foil (0.027 g, 1 mmol) in dry THF (4 mL) were successively added allyl bromide (0.27 mL, 3 mmol) and TiCl4 (5.4 mL, 0.05 mmol) at rt. After being stirred for 8 h, the mixture was poured into 5% aq NaOH, worked up, and purified by column chromatography [silica gel, hexane/benzene (CAUTION:carcinogen)]; yield: 0.17 g (83%).

7.1.1.4 Method 4: Aluminum–Lead System

An aluminum–lead bimetallic system can be used to carry out reductive addition of carbon tetrachloride, carbon tetrabromide, bromotrichloromethane, trichloroacetamide, or trichloroacetonitrile to aldehydes (▶ Scheme 4).[10] It is noteworthy that commercially available lead powder (>99.9% pure) alone is not effective at all for this reductive addition. This suggests that lead(0), freshly generated on the aluminum surface, is important for the coupling reaction. For example, in the presence of 1.2 equivalents of aluminum and catalytic lead(II) bromide (Al/PbBr2 12:1), 2, 2, 2-trichloro-1-(4-chlorophenyl)ethanol (6) is prepared in 94% yield from 4-chlorobenzaldehyde and carbon tetrachloride (▶ Scheme 4).[11,12] The combination of aluminum(0) and a catalytic amount of lead(II) chloride or lead powder also gives trichloroethanol derivative 6 in comparable yields.[11–13] The reaction of carbon tetrachloride with 4-chlorobenzaldehyde has also been attempted with combinations of aluminum foil with tin(II) chloride, bismuth(III) chloride, germanium(IV) chloride, or zinc(II) chloride (10 mol% each) under similar conditions.[12] However, the starting material is recovered almost quantitatively in all cases except when 50 mol% tin(II) chloride is used.

Subsequent 1, 2-elimination of the halogen atom and hydroxy group from the coupling products is also possible with the aluminum–lead bimetallic system. Similar systems composed of aluminum/lead/aluminum trichloride and aluminum/lead(II) bromide are used for Barbier-type allylation of acetals with allyl bromide and reductive homocou-pling of imines, respectively.[11,12]

▶ Scheme 4 Trichloromethylation of an Aromatic Aldehyde Catalyzed by a Low-Valent Lead Reagent Generated by Aluminum[11,12]

2, 2, 2-Trichloro-1-(4-chlorophenyl)ethanol (6);Typical Procedure:[11,12]

Into a mixture of PbBr2 (37 mg, 0.1 mmol) and finely cut Al foil (32 mg, 1.2 mmol) in DMF (5 mL) was added 4-chlorobenzaldehyde (141 mg, 1.0 mmol) and CCl4 (0.20 mL, 2.0 mmol) (CAUTION:toxic). The mixture was stirred at rt for 3 h, until most of the 4-chlorobenzaldehyde was consumed. The reaction was quenched with 5% aq HCl, and the mixture was extracted with EtOAc (5 × 6 mL). The combined extracts were washed with aq NaHCO3 (6 mL) and brine (4 × 6 mL), dried (Na2SO4