Science of Synthesis Knowledge Updates 2016 Vol. 1 E-Book

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

Seitenzahl: 964

Veröffentlichungsjahr: 2016

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.

everal annual volumes updating content across all categories ensure that you always have access to state-of-the-art synthetic methodology.

This update volume contains: A major update on the synthesis of pyridines, pyridinium salts, and pyridine N-oxides (D. Spitzner) covering new synthetic approaches as well as improvements and extensions to previously reported methods.

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 expertevaluated 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.

The Editorial Board

July 2010

E. M. Carreira (Zurich, Switzerland)

C. P. Decicco (Princeton, USA)

A. Fuerstner (Muelheim, Germany)

G. Koch (Basel, Switzerland)

G. A. Molander (Philadelphia, USA)

E. Schaumann (Clausthal-Zellerfeld, Germany)

M. Shibasaki (Tokyo, Japan)

E. J. Thomas (Manchester, UK)

B. M. Trost (Stanford, USA)

Abstracts

15.1.4 Pyridines

D. Spitzner

This chapter is an update to the 2004 Science of Synthesis contribution on pyridines. It covers the literature up until early 2016. This update covers the synthesis of pyridines, pyridine 1-oxides, pyridinium salts, and some di- and tetrahydropyridines. Pyridines and their derivatives are substructures in many natural products, drugs, pesticides, and other molecules of interest, and numerous methods are available for their synthesis.

Keywords: pyridines • pyridine 1-oxides • pyridinium salts • heterocycles • heteroaromatics • cyclization • aromatization

34.1.2.6 Synthesis by Substitution of Metals

M. Shevchuk and G.-V. Rçschenthaler

This update summarizes recent developments in the synthesis of organic compounds with one C—F bond by substitution of metals. Because classical organometallic reagents, such as organolithiums and organomagnesiums, are highly basic and tend to decompose typical “F+” sources, their application as substrates for electrophilic fluorination has been limited. Instead, new approaches utilizing either mild organometalloid precursors, such as organoboron compounds, or transition-metal-mediated transformations have been brought into focus. These state-of-the-art approaches form the main part of this review.

Keywords: boron compounds • carbon—metal bonds • deboronation • desilylation • electrophilic substitution • fluorine compounds • fluorination • fullerenes • radical reactions • transition metals

34.1.3.4 Synthesis by Substitution of Carbon Functionalities

J. Desroches and J.-F. Paquin

This chapter is an update to the earlier Science of Synthesis contribution describing methods for the synthesis of alkyl fluorides by substitution of carbon functionalities. It focuses on the literature published in the period 2000–2015.

Keywords: carbon—carbon bond cleavage • decarboxylation • fluorination • fluorine compounds • photochemistry • cycloalkane ring opening

34.1.4.2.9 Synthesis by Substitution of Hydroxy Groups in Alcohols

M. Vandamme and J.-F. Paquin

This chapter is an update to the earlier Science of Synthesis contribution describing methods for the synthesis of fluoroalkanes by substitution of hydroxy groups in alcohols. It focuses on the literature published in the period 2005–2015.

Keywords: nucleophilic substitution • fluorodehydroxylation • alcohols • fluoroalkanes • elimination side-reactions • stereoselectivity • chemoselectivity

34.5.2 Propargylic Fluorides

J.-D. Hamel and J.-F. Paquin

This chapter is an update to the earlier Science of Synthesis contribution describing methods for the synthesis of propargylic fluorides. It focuses on the literature published in the period 2006–2015.

Keywords: allenoates • allenylsilanes • dehydroxyfluorination • electrophilic fluorination • fluorinated sulfones • homologation • nucleophilic fluorination • organocatalysis • propargylic alcohols • stereoselectivity

34.6.2 Benzylic Fluorides

P. A. Champagne, M. Drouin, and J.-F. Paquin

This chapter is an update to the earlier Science of Synthesis contribution of 2005 describing methods for the synthesis of benzylic fluorides. It focuses on the literature published in the period 2005–2015.

Keywords: fluorination • fluorine compounds • benzylic compounds • regioselectivity • stereoselectivity

Science of Synthesis Knowledge Updates 2016/1

Preface

Abstracts

Table of Contents

15.1.4 Pyridines (Update 2016)

D. Spitzner

34.1.2.6 Synthesis by Substitution of Metals (Update 2016)

M. Shevchuk and G.-V. Röschenthaler

34.1.3.4 Synthesis by Substitution of Carbon Functionalities (Update 2016)

J. Desroches and J.-F. Paquin

34.1.4.2.9 Synthesis by Substitution of Hydroxy Groups in Alcohols (Update 2016)

M. Vandamme and J.-F. Paquin

34.5.2 Propargylic Fluorides (Update 2016)

J.-D. Hamel and J.-F. Paquin

34.6.2 Benzylic Fluorides (Update 2016)

P. A. Champagne, M. Drouin, and J.-F. Paquin

Author Index

Abbreviations

Table of Contents

Volume 15: Six-Membered Hetarenes with One Nitrogen or Phosphorus Atom

15.1 Product Class 1: Pyridines

15.1.4 Pyridines

D. Spitzner

15.1.4 Pyridines

15.1.4.1 Pyridines

15.1.4.1.1 Synthesis by Ring-Closure Reactions

15.1.4.1.1.1 By Formation of Two N—C and Two C—C Bonds

15.1.4.1.1.1.1 Fragments C—C, C—C, N, and C

15.1.4.1.1.1.1.1 Method 1: Synthesis from 1,3-Diketones or 3-Oxo Esters, Aldehydes, and Ammonia or Amines, with Subsequent Oxidation (Hantzsch Pyridine Synthesis)

15.1.4.1.1.1.1.1.1 Variation 1: Polymer-Assisted Hantzsch Cyclocondensation and Enantioselective Organocatalytic Hantzsch Synthesis

15.1.4.1.1.1.1.1.2 Variation 2: From Oxonitriles, Aldehydes, and Ammonium Acetate

15.1.4.1.1.1.1.1.3 Variation 3: From Ketones, N-Phenacylpyridinium Compounds, Aldehydes, and Ammonium Acetate (Modified Kröhnke Method). 11

15.1.4.1.1.1.1.1.4 Variation 4: From Aromatic Ketones and Ammonium Acetate by Metal-Free Condensation

15.1.4.1.1.1.1.1.5 Variation 5: 4-Unsubstituted Pyridines from Enaminones and Ammonium Chloride

15.1.4.1.1.1.1.2 Method 2: Synthesis from Acryloyl Azides by Curtius Rearrangement

15.1.4.1.1.1.1.3 Method 3: Synthesis from an Arylaldehyde, Acetoacetates, and Ammonium Acetate

15.1.4.1.1.1.1.4 Method 4: Synthesis from Acetaldehydes and a Nitrogen Donor

15.1.4.1.1.1.2 Fragments N, C—C—C, C, and C

15.1.4.1.1.1.2.1 Method 1: Three-Component Coupling of an Allyl Alcohol, an Aldehyde, and Lithium Hexamethyldisilazanide, Followed by Metallacycle-Mediated Cyclization

15.1.4.1.1.1.2.2 Method 2: Synthesis from Ketones and the Vilsmeier–Haack Reagent

15.1.4.1.1.2 By Formation of One N—C and Three C—C Bonds

15.1.4.1.1.2.1 Fragments C—C, N—C, C, and C

15.1.4.1.1.2.1.1 Method 1: Synthesis from Ketenimines, Aldehydes, Nitriles, and Diethyl Methylphosphonate

15.1.4.1.1.3 By Formation of Two N—C Bonds and One C—C Bond

15.1.4.1.1.3.1 Fragments C—C—C, C—C, and N

15.1.4.1.1.3.1.1 Method 1: Synthesis from Acyl Enamines, β-Dicarbonyl Compounds, and Hydroxylamine or Ammonium Salts

15.1.4.1.1.3.1.1.1 Variation 1: From Ketene Dithioacetals, Ketones, and an Ammonium Salt. 20

15.1.4.1.1.3.1.1.2 Variation 2: From Ketones, α,β-Unsaturated Aldehydes or Ketones, and Ammonium Salts

15.1.4.1.1.3.1.1.3 Variation 3: From 2-Pyrrolidinoacetophenones with Chalcones

15.1.4.1.1.3.1.1.4 Variation 4: From Nitroalkenes, Amines, and Enones by Condensation

15.1.4.1.1.3.1.2 Method 2: Synthesis from Acylpyridinium Compounds (Kröhnke Compounds), α,β-Unsaturated Ketones, and an Ammonium Salt. 23

15.1.4.1.1.3.1.3 Method 3: Synthesis from α,β-Unsaturated Ketones and Ammonium Acetate

15.1.4.1.1.3.1.4 Method 4: 2-Arylpyridines Using One-Pot 6π-Azaelectrocyclization

15.1.4.1.1.3.1.5 Method 5: Synthesis from Ynones, Ketones, and Ammonium Salts (Bohlmann–Rahtz-Type Pyridine Synthesis and Bagley Variation)

15.1.4.1.1.3.1.6 Method 6: Synthesis from Propargyl Enol Ethers and O-Methylhydroxylamine Hydrochloride

15.1.4.1.1.3.1.7 Method 7: Palladium-Catalyzed Sequential Coupling/Imination/Annulation of 3-Bromoarene-2-carbaldehydes with Terminal Acetylenes and Ammonium Acetate

15.1.4.1.1.3.1.8 Method 8: Synthesis from 1-Methyl-3,5-dinitropyridin-2-one as C—C—C Unit

15.1.4.1.1.3.1.9 Method 9: Synthesis from a Dialdehyde and Hydroxylamine

15.1.4.1.1.3.1.10 Method 10: Synthesis from a Terminal Propargyl Alcohol, an Enamine, and Ammonium Chloride

15.1.4.1.1.3.1.11 Method 11: Synthesis from 3-Aryl-3-oxohydrazonopropanals, 3-Oxo-3-phenylpropanenitrile, and Ammonium Acetate

15.1.4.1.1.3.1.12 Method 12: Synthesis of Tetrasubstituted Pyridines from 3-Haloacrylaldehydes, Ketones, and tert-Butylamine

15.1.4.1.1.4 By Formation of One N—C Bond and Two C—C Bonds

15.1.4.1.1.4.1 Fragments N—C, C—C, and C—C

15.1.4.1.1.4.1.1 Method 1: Synthesis from Nitriles and Alkynes via an Azametallacyclopentadiene

15.1.4.1.1.4.1.2 Method 2: Rhodium-Catalyzed [2 + 2 + 2] Cycloaddition

15.1.4.1.1.4.1.2.1 Variation 1: Rhodium-Catalyzed [2 + 2 + 2] Cycloaddition of Oximes and Diynes

15.1.4.1.1.4.1.3 Method 3: Cobalt-, Iron-, Nickel-, or Iridium-Catalyzed [2 +2+2] Cycloaddition

15.1.4.1.1.4.1.3.1 Variation 1: Metalated Pyridines from Two Alkynes, a Nitrile, and Titanium (IV) Alkoxides

15.1.4.1.1.4.1.3.2 Variation 2: Pyridines via Solid-Supported [2 + 2 + 2] Cyclotrimerization

15.1.4.1.1.4.1.4 Method 4: Synthesis from α-Amino Acids and Aldehydes by Decarboxylative Cyclization

15.1.4.1.1.4.1.5 Method 5: Synthesis from Imines and Haloalkenes by One-Pot Cross Coupling

15.1.4.1.1.4.1.6 Method 6: Synthesis from Nitriles and Alkynes under Metal-Free Conditions

15.1.4.1.1.4.1.7 Method 7: Synthesis from a Nitrile, an Alkyne, and Allyl 4-Tolyl Sulfoxide

15.1.4.1.1.4.1.8 Method 8: Synthesis from a Vinyl Ether and a Cyano Alkynamide

15.1.4.1.1.4.1.9 Method 9: Tetrasubstituted Pyridines from Acylmethyl Azides and Acetylenedicarboxylates

15.1.4.1.1.4.1.10 Method 10: Copper-Catalyzed Domino Synthesis of Pentasubstituted Pyridines from Malononitrile and Alkynes

15.1.4.1.1.4.2 Fragments N—C—C, C—C, and C

15.1.4.1.1.4.2.1 Method 1: Chlorotrimethylsilane-Promoted Three-Component Coupling Reaction of a Functionalized Enamine, an Acetal, and an Alkyne

15.1.4.1.1.4.2.2 Method 2: Synthesis from Enamines and Triethyl Orthoformate by Hafnium(IV) Trifluoromethanesulfonate Catalyzed Annulation

15.1.4.1.1.4.2.2.1 Variation 1: From Oxime Esters, Aldehydes, and Activated Methylene Compounds

15.1.4.1.1.4.2.3 Method 3: Synthesis from a Lithiated Alkylsilane, a Nitrile, and a Fluoroalkene

15.1.4.1.1.4.2.4 Method 4: Synthesis from Malononitrile, Aldehydes, and Nucleophiles

15.1.4.1.1.4.2.5 Method 5: Synthesis from Malononitrile, Dimethylformamide, and Ketones (Vilsmeier–Haack Reaction)

15.1.4.1.1.4.2.6 Method 6: Copper-Catalyzed Coupling of Oxime Acetates with Aldehydes

15.1.4.1.1.4.2.6.1 Variation 1: Synthesis from an Oxime Ester, Malononitrile, and Aldehydes

15.1.4.1.1.4.2.7 Method 7: Synthesis from N-Vinylic Phosphazenes, α,β-Unsaturated Aldehydes, and Enamines by [4 + 2] Cycloaddition

15.1.4.1.1.4.2.8 Method 8: Ruthenium-Catalyzed Cyclization of Ketoxime Acetates with N, N-Dimethylformamide

15.1.4.1.1.4.3 Fragments C—C—C, N—C, and C

15.1.4.1.1.4.3.1 Method 1: Synthesis from Nitriles, Fluorinated Acids, and Lithiated Methoxyallene

15.1.4.1.1.4.3.2 Method 2: Synthesis from Nitriles, a 1,3-Enyne, and Carbanions in a One-Pot Reaction

15.1.4.1.1.4.3.3 Method 3: Pyridin-4-amines from α-Azido Vinyl Ketones, Aldehydes, and Methylamines by a One-Pot Procedure

15.1.4.1.1.4.3.3.1 Variation 1: N-Tosylpiperidinones by a Four-Component One-Pot Synthesis

15.1.4.1.1.5 By Formation of Three C—C Bonds

15.1.4.1.1.5.1 Fragments C—N—C, C—C, and C

15.1.4.1.1.5.1.1 Method 1: Synthesis from Arynes, Isocyanides, and Terminal Alkynes

15.1.4.1.1.6 By Formation of Two N—C Bonds

15.1.4.1.1.6.1 Fragments C—C—C—C—C and N

15.1.4.1.1.6.1.1 Method 1: Synthesis from 2-Alkyl-5-amino-1-tert-butyliminopentadienes and Ammonium Salts

15.1.4.1.1.6.1.2 Method 2: Synthesis from 1,5-Dicarbonyl Compounds and Ammonia or Ammonium Salts