Science of Synthesis Knowledge Updates 2011 Vol. 4 E-Book

• Herausgeber: Thieme
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1114

Veröffentlichungsjahr: 2014

Beschreibung

The Science of Synthesis Editorial Board,together with the volume editors and authors, is constantly reviewing the whole field of synthetic organic chemistry as presented in Science of Synthesis and evaluating significant developments in synthetic methodology. Four annual volumes updating content across all categories ensure that you always have access to state-of-the-art synthetic methodology.

Content of this volume: Organometallic Complexes of Scandium, Yttrium, and the Lanthanides, Metallocene Complexes with Bis(trimethylsilyl)acetylene, Titanocene-Bis(trimethylsilyl)acetylene Complexes, Zirconocene-Bis(trimethylsilyl)acetylene Complexes, Hafnocene Bis(trimethylsilyl)acetylene Complexes, Boron Compounds, Aluminum Alkoxides and Phenoxides, Aluminum Amides, Dearomatization Reactions Using Organolithiums, Carbolithiation of Carbon-Carbon Multiple Bonds, Pyrazines, Six-Membered Hetarenes with More than Three Heteroatoms, Nitriles, Oximes.

Leseprobe

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 the pace and breadth of research intensifies, organic synthesis is playing an increasingly central role in the discovery process within all imaginable areas of science: from pharmaceuticals, agrochemicals, and materials science to areas of biology and physics, the most impactful investigations are becoming more and more molecular. As an enabling science, synthetic organic chemistry is uniquely poised to provide access to compounds with exciting and valuable new properties. Organic molecules of extreme complexity can, given expert knowledge, be prepared with exquisite efficiency and selectivity, allowing virtually any phenomenon to be probed at levels never before imagined. With ready access to materials of remarkable structural diversity, critical studies can be conducted that reveal the intimate workings of chemical, biological, or physical processes with stunning detail.

The sheer variety of chemical structural space required for these investigations and the design elements necessary to assemble molecular targets of increasing intricacy place extraordinary demands on the individual synthetic methods used. They must be robust and provide reliably high yields on both small and large scales, have broad applicability, and exhibit high selectivity. Increasingly, synthetic approaches to organic molecules must take into account environmental sustainability. Thus, atom economy and the overall environmental impact of the transformations are taking on increased importance.

The need to provide a dependable source of information on evaluated synthetic methods in organic chemistry embracing these characteristics was first acknowledged over 100 years ago, when the highly regarded reference source Houben–Weyl Methoden der Organischen Chemie was first introduced. Recognizing the necessity to provide a modernized, comprehensive, and critical assessment of synthetic organic chemistry, in 2000 Thieme launched Science of Synthesis, Houben–Weyl Methods of Molecular Transformations. This effort, assembled by almost 1000 leading experts from both industry and academia, provides a balanced and critical analysis of the entire literature from the early 1800s until the year of publication. The accompanying online version of Science of Synthesis provides text, structure, substructure, and reaction searching capabilities by a powerful, yet easy-to-use, intuitive interface.

From 2010 onward, Science of Synthesis is being updated quarterly with high-quality content via Science of Synthesis Knowledge Updates. The goal of the Science of Synthesis Knowledge Updates is to provide a continuous review of the field of synthetic organic chemistry, with an eye toward evaluating and analyzing significant new developments in synthetic methods. A list of stringent criteria for inclusion of each synthetic transformation ensures that only the best and most reliable synthetic methods are incorporated. These efforts guarantee that Science of Synthesis will continue to be the most up-to-date electronic database available for the documentation of validated synthetic methods.

Also from 2010, Science of Synthesis includes the Science of Synthesis Reference Library, comprising volumes covering special topics of organic chemistry in a modular fashion, with six main classifications: (1) Classical, (2) Advances, (3) Transformations, (4) Applications, (5) Structures, and (6) Techniques. Titles will include Stereoselective Synthesis, Water in Organic Synthesis, and Asymmetric Organocatalysis, among others. With expert-evaluated content focusing on subjects of particular current interest, the Science of Synthesis Reference Library complements the Science of Synthesis Knowledge Updates, to make Science of Synthesis the complete information source for the modern synthetic chemist.

The overarching goal of the Science of Synthesis Editorial Board is to make the suite of Science of Synthesis resources the first and foremost focal point for critically evaluated information on chemical transformations for those individuals involved in the design and construction of organic molecules.

Throughout the years, the chemical community has benefited tremendously from the outstanding contribution of hundreds of highly dedicated expert authors who have devoted their energies and intellectual capital to these projects. We thank all of these individuals for the heroic efforts they have made throughout the entire publication process to make Science of Synthesis a reference work of the highest integrity and quality.

July 2010

The Editorial Board

E. M. Carreira (Zurich, Switzerland)

C. P. Decicco (Princeton, USA)

A. Fuerstner (Muelheim, Germany)

G. A. Molander (Philadelphia, USA)

P. J. Reider (Princeton, USA)

E. Schaumann (Clausthal-Zellerfeld, Germany)

M. Shibasaki (Tokyo, Japan)

E. J. Thomas (Manchester, UK)

B. M. Trost (Stanford, USA)

Abstracts

2.12.15 Organometallic Complexes of Scandium, Yttrium, and the Lanthanides

P. Dissanayake, D. J. Averill, and M. J. Allen

This manuscript is an update to the existing Science of Synthesis chapter on organometallic complexes of lanthanides. It summarizes the synthesis of β-hydroxycarbonyl compounds using lanthanide-containing catalysts in Mukaiyama aldol reactions. Early investigations as well as recent improvements to lanthanide-containing catalysts with respect to substrate scope and enantioselectivity are included.

Keywords: aldol reaction · catalysis · β-hydroxycarbonyl · lanthanide · Mukaiyama

2.14 Product Class 14: Group 4 Metallocene Complexes with Bis(trimethylsilyl)acetylene

T. Beweries and U. Rosenthal

This manuscript describes the methods for the synthesis and application of group 4 metallocene–bis(trimethylsilyl)acetylene complexes. Recent interest in this area has been generated by the fact that metallocenes play an important role in numerous catalytic and stoichiometric applications, including the formation of metallacycles, which can serve as model compounds for such highly interesting reactions as the oligomerization of ethene to linear alpha alkenes.

Keywords: alkyne complexes · titanocenes · zirconocenes · hafnocenes · metallacycles

6.1.7.11 Hydroxyboranes

D. G. Hall and H. Zheng

This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the preparation and application of organoboronic acids (hydroxyboranes) in organic synthesis. It focuses on the literature published in the period 2002–2011.

Keywords: boronic acids · boronic esters · borylation · boronic ester hydrolysis · boronic acid catalysis · cross-coupling reaction · C—C bond formation · C—X bond formation · C—H borylation · hydroxyboranes · organoboronic acids · phase-switch purification

7.1.4.7 Aluminum Alkoxides and Phenoxides

K. Ohmatsu and T. Ooi

This manuscript is an update to the earlier Science of Synthesis contribution describing the synthesis of aluminum alkoxides and phenoxides. It focuses on the literature published in the period 1999–2010.

Keywords: alkoxides · aluminum compounds · asymmetric catalysis · carbonyl compounds · Lewis acid catalysis · phenoxides

7.1.7.15 Aluminum Amides

K. Ohmatsu and T. Ooi

This manuscript is an update to the earlier Science of Synthesis contribution on the synthesis of aluminum amides. It focuses on the literature published in the period 1999–2010.

Keywords: aluminum compounds · amides · asymmetric catalysis · carbonyl compounds · coupling reactions · Lewis acid catalysis

8.1.29 Dearomatization Reactions Using Organolithiums

G. Lemière and J. Clayden

Addition of organolithiums to aromatic rings has emerged as a convenient method for the rapid construction of functionalized carbocyclic and heterocyclic compounds. These dearomatization reactions of readily available activated or unactivated aromatic rings often occur with a high degree of selectivity. Developments in the intramolecular version of this process known as dearomatizing cyclization have allowed access to various polycyclic frameworks with well-defined relative stereochemistry. Several strategies have been employed to carry out asymmetric organolithium-mediated dearomatizations efficiently and some of them have been used as key steps in the synthesis of natural compounds.

Keywords: organolithium · dearomatization · dearomatizing addition · dearomatizing cyclization · rearrangements · stereospecificity

8.1.30 Carbolithiation of Carbon–Carbon Multiple Bonds

E. Lete and N. Sotomayor

This chapter describes relevant synthetic applications of carbolithiation reactions of alkenes and alkynes. Both inter- and intramolecular reactions are discussed, including also enantioselective transformations.

Keywords: carbolithiation · lithiation · lithium compounds · carbanions · carbon–carbon double bonds · carbon–carbon triple bonds · cyclization · diastereoselectivity · enantioselectivity · intramolecular reactions

16.14.5 Pyrazines

N. Sato

This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the synthesis of pyrazines. It focuses on the literature published in the period 2002–2010, together with some selected references for 2011.

Keywords: pyrazines · cyclocondensation · dimerization · cyclization · metalation · halo compounds · cross-coupling reactions · Suzuki coupling · palladium catalyst · microwave irradiation

17.3.4 Six-Membered Hetarenes with More than Three Heteroatoms

S. L. Castle

This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the synthesis of aromatic tetrazines. It focuses on the literature published in the period 2003–2010.

Keywords: nitrogen heterocycles · tetrazines · annulation · aromatization · cross-coupling reactions · dimerization · nucleophilic aromatic substitution

19.5.16 Asymmetric Synthesis of Nitriles

W. T. Wang, L. L. Lin, X. H. Liu, and X. M. Feng

This manuscript provides an update to the methods for the synthesis of chiral nitriles previously covered in Science of Synthesis, Section 19.5. It focuses on the literature published in the period 2003–2011.

Keywords: asymmetric synthesis · cyanation · nitriles · cyanohydrins · cyanosilylation · α-amino nitriles · hydrocyanation · conjugate addition.

27.15 Product Class 15: Oximes

S. Chiba and K. Narasaka

The chemical reactions of oximes are much more diverse than those of N-substituted imines and carbonyl compounds such as ketones. This wide range in the chemical reactivity of oximes is derived from their unique chemical structure, which includes three different atoms (carbon, nitrogen, and oxygen) and a polarized C=N bond. In this chapter, preparation methods and synthetic reactions of oximes and their derivatives are reviewed, covering not only classical but also more-recent literature precedents.

Keywords: oximes · amination · amino compounds · azaheterocycles

Science of Synthesis Knowledge Updates 2010/3

Preface

Abstracts

Table of Contents

2.12.15 Organometallic Complexes of Scandium, Yttrium, and the Lanthanides (Update 2011)

P. Dissanayake, D. J. Averill, and M. J. Allen

2.14 Product Class 14: Group 4 Metallocene Complexes with Bis(trimethylsilyl)acetylene

T. Beweries and U. Rosenthal

6.1.7.11 Hydroxyboranes (Update 2011)

D. G. Hall and H. Zheng

7.1.4.7 Aluminum Alkoxides and Phenoxides (Update 2011)

K. Ohmatsu and T. Ooi

7.1.7.15 Aluminum Amides (Update 2011)

K. Ohmatsu and T. Ooi

8.1.29 Dearomatization Reactions Using Organolithiums

G. Lemière and J. Clayden

8.1.30 Carbolithiation of Carbon–Carbon Multiple Bonds

E. Lete and N. Sotomayor

16.14.5 Pyrazines (Update 2011)

N. Sato

17.3.4 Six-Membered Hetarenes with More than Three Heteroatoms (Update 2011)

S. L. Castle

19.5.16 Asymmetric Synthesis of Nitriles

W. T. Wang, L. L. Lin, X. H. Liu, and X. M. Feng

27.15 Product Class 15: Oximes

S. Chiba and K. Narasaka

Author Index

Abbreviations

Table of Contents

Volume 2: Compounds of Groups 7–3 (Mn…, Cr…, V…, Ti…, Sc…, La…, Ac…)

2.12 Product Class 12: Organometallic Complexes of Scandium, Yttrium, and the Lanthanides

2.12.15 Organometallic Complexes of Scandium, Yttrium, and the Lanthanides

P. Dissanayake, D. J. Averill, and M. J. Allen

2.12.15 Organometallic Complexes of Scandium, Yttrium, and the Lanthanides

2.12.15.1 Lanthanide-Catalyzed Mukaiyama Aldol Reactions

2.12.15.1.1 Method 1: Non-enantioselective Formation of β-Hydroxycarbonyls

2.12.15.1.2 Method 2: Enantioselective Formation of β-Hydroxycarbonyls

2.12.15.1.2.1 Variation 1: In an Organic Solvent

2.12.15.1.2.2 Variation 2: In an Aqueous Solvent

2.14 Product Class 14: Group 4 Metallocene Complexes with Bis(trimethylsilyl)acetylene

T. Beweries and U. Rosenthal

2.14 Product Class 14: Group 4 Metallocene Complexes with Bis(trimethylsilyl)acetylene

2.14.1 Product Subclass 1: Titanocene–Bis(trimethylsilyl)acetylene Complexes

Synthesis of Product Subclass 1

2.14.1.1 Method 1: Reduction of a Dichlorobis(η5-cyclopentadienyl)titanium Derivative in the Presence of Bis(trimethylsilyl)acetylene

2.14.1.1.1 Variation 1: Reduction and Intramolecular Dehydrocoupling of Cyclopentadienyl Fragments

2.14.1.2 Method 2: Methane Elimination from Bis(η5-cyclopentadienyl)dimethyltitanium(IV)

Applications of Product Subclass 1 in Organometallic Reactions

2.14.1.3 Method 3: Reactions with Brønsted Acids

2.14.1.3.1 Variation 1: Reaction with Methanol

2.14.1.4 Method 4: Titanocene–Bis(trimethylsilyl)acetylene Complexes in the Formation of Metallacycles

2.14.1.4.1 Variation 1: Formation of Five-Membered Group 4 Metallacycles

2.14.1.4.2 Variation 2: Formation of Six-Membered Metallacycles

2.14.1.4.3 Variation 3: Formation of Three-Membered Aza-metallacycles

2.14.1.4.4 Variation 4: Formation of Four- and Five-Membered Aza-metallacycles

2.14.1.4.5 Variation 5: Coupling Reactions of Dichlorophosphines and the Formation of Phospha-metallacycles

2.14.1.4.6 Variation 6: Formation of Stiba-metallacycles

2.14.1.4.7 Variation 7: Formation of Four-Membered Thia-metallacycles

2.14.1.4.8 Variation 8: Formation of Four-Membered Selena-metallacycles

2.14.1.5 Method 5: Titanocene–Bis(trimethylsilyl)acetylene Complexes in Supramolecular Chemistry

2.14.1.5.1 Variation 1: Dehydrogenative Coupling

2.14.1.6 Method 6: Titanocene–Bis(trimethylsilyl)acetylene Complexes in Bond-Activation Reactions

2.14.1.6.1 Variation 1: Dinitrogen Activation

2.14.1.6.2 Variation 2: C—F Bond Activation

2.14.1.6.3 Variation 3: C—C Single-Bond Metathesis

2.14.1.7 Method 7: Catalytic Hydroamination of Alkynes

2.14.1.8 Method 8: Catalytic Dehydrogenation of Dimethylamine Borane

2.14.1.9 Method 9: Oxidation Reactions

2.14.1.10 Method 10: Reactions with Alkynes: Alkyne Substitution Reactions

2.14.1.10.1 Variation 1: Reactions with Alkynylsilanes

2.14.1.10.2 Variation 2: Reactions with Polyynes

2.14.1.11 Method 11: Lewis Base Exchange

2.14.1.12 Method 12: Reactions with Carbon Dioxide

2.14.2 Product Subclass 2: Zirconocene–Bis(trimethylsilyl)acetylene Complexes

Synthesis of Product Subclass 2

2.14.2.1 Method 1: Reduction of a Dichlorobis(η5-cyclopentadienyl)zirconium(IV) in the Presence of Bis(trimethylsilyl)acetylene

2.14.2.1.1 Variation 1: By Ligand Substitution

Applications of Product Subclass 2 in Organometallic Reactions

2.14.2.2 Method 2: Reactions with Brønsted Acids

2.14.2.3 Method 3: Reactions with Internal Alkynes

2.14.2.3.1 Variation 1: Alkyne Substitutions

2.14.2.3.2 Variation 2: Formation of Zirconacyclopenta-2,4-dienes

2.14.2.3.3 Variation 3: Macrocyclization

2.14.2.3.4 Variation 4: Formation of Pentakis(pentafluorophenyl)borole

2.14.2.4 Method 4: Reactions with Terminal Alkynes

2.14.2.5 Method 5: Reactions with Carbonyl Compounds

2.14.2.6 Method 6: Zirconocene–Bis(trimethylsilyl)acetylene Complexes in the Formation of Metallacycles

2.14.2.6.1 Variation 1: Formation of Five-Membered Metallacycles

2.14.2.6.2 Variation 2: Formation of Three-Membered Aza-metallacycles

2.14.2.6.3 Variation 3: Formation of Five-Membered Aza-metallacycles

2.14.2.6.4 Variation 4: Formation of Five- and Seven-Membered Oxa-metallacycles

2.14.2.6.5 Variation 5: Formation of Four-Membered Thia-metallacycles

2.14.2.7 Method 7: Zirconocene–Bis(trimethylsilyl)acetylene Complexes in Bond-Activation Reactions

2.14.2.7.1 Variation 1: Dinitrogen Activation

2.14.2.7.2 Variation 2: C—F versus C—H Bond Activation

2.14.2.7.3 Variation 3: C—H Bond Activation

2.14.3 Product Subclass 3: Hafnocene Bis(trimethylsilyl)acetylene Complexes

Synthesis of Product Subclass 3

2.14.3.1 Method 1: Reduction of a Dichlorobis(η5-cyclopentadienyl)hafnium in the Presence of Bis(trimethylsilyl)acetylene

2.14.3.2 Method 2: Synthesis from Dibutylbis(η5-cyclopentadienyl)hafnium(IV)

Applications of Product Subclass 3 in Organometallic Reactions

2.14.3.3 Method 3: Reactions with Alkenes

Volume 6: Boron Compounds

6.1 Product Class 1: Boron Compounds

6.1.7.11 Hydroxyboranes

D. G. Hall and H. Zheng

6.1.7.11 Hydroxyboranes

6.1.7.11.1 Method 1: Synthesis by Metal-Catalyzed C—H Borylation

6.1.7.11.1.1 Variation 1: Aromatic C—H Borylation

6.1.7.11.1.2 Variation 2: Dehydrogenative Borylation

6.1.7.11.2 Method 2: Synthesis by Borylative Cross Coupling

6.1.7.11.2.1 Variation 1: Palladium-Catalyzed Borylative Cross Coupling

6.1.7.11.2.2 Variation 2: Nickel- and Copper-Catalyzed Borylative Cross Coupling

6.1.7.11.2.3 Variation 3: Metal-Free Borylative Cross Coupling

6.1.7.11.3 Method 3: Synthesis by Direct Borylation with Borenium Cations

6.1.7.11.4 Method 4: Synthesis by Addition Reactions with Diboron Species

6.1.7.11.4.1 Variation 1: Addition of Diboron Species to Carbonyl or Thiocarbonyl Groups, or Aldimines

6.1.7.11.4.2 Variation 2: β-Boration of α,β-Unsaturated Carbonyl Derivatives

6.1.7.11.5 Method 5: Synthesis by Hydrolysis of Boronates or Trifluoro(organo)borates

6.1.7.11.6 Method 6: Chemoselective Chemical Transformations of Parent Free Boronic Acids or Derivatives

6.1.7.11.7 Method 7: Applications as Catalysts or Stoichiometric Reaction Promoters

6.1.7.11.7.1 Variation 1: Activation of Carboxylic Acids

6.1.7.11.7.2 Variation 2: Activation of Alcohols

6.1.7.11.7.3 Variation 3: Activation of Carbonyl Groups

6.1.7.11.7.4 Variation 4: Use as Stoichiometric Reaction Promoters

6.1.7.11.8 Method 8: Applications in Carbon—Heteroatom Bond Formation

6.1.7.11.8.1 Variation 1: C—O Bond Formation