Science of Synthesis Knowledge Updates 2014 Vol. 3 E-Book

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

Seitenzahl: 999

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:

Five#Five-Fused Hetarenes with One Heteroatom in Each Ring; One Oxygen and One Nitrogen or Phosphorus Atom; One Sulfur, Selenium, or Tellurium Atom and One Nitrogen or Phosphorus Atom; Carbon Dioxide, Carbonyl Sulfide, Carbon Disulfide, Isocyanates, Isothiocyanates, Carbodiimides, and Their Selenium, Tellurium, and Phosphorus Analogues; 1,1-Dihaloalk-1-enes; Bis(heteroatom-functionalized) Acetylenes; 1-Haloalk-1-ynes and Alk-1-yn-1-ols; Diazo Compounds; Alkaneselenolates of Group 3#12 Metals; Cyclic Alkaneselenolates of Group 3#12 Metals; Alkanetellurolates of Group 3#12 Metals; Cyclic Alkanetellurolates of Group 3#12 Metals.

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.

The Editorial Board

July 2010

E. M. Carreira (Zurich, Switzerland)

C. P. Decicco (Princeton, USA)

A. Fuerstner (Muelheim, Germany)

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

10.21 Product Class 21: Five–Five-Fused Hetarenes with One Heteroatom in Each Ring

S. P. StanforthThis is a new chapter for Science of Synthesis which describes methods for the synthesis of four classes of hetaryl[n,m-p]hetarenes from acyclic precursors. The functionalization of these heterocycles by either the introduction of new groups or the modification of existing substituents is also discussed.

Keywords: heterocycles · hetaryl[n,m-p]hetarenes · diheteropentalenes · non-classical heteropentalenes · thieno[n,m-p]thiophenes

17.1.2.5 One Oxygen and One Nitrogen or Phosphorus Atom

R. A. Aitken and A. MeehanThis chapter is an update of the earlier Science of Synthesis contribution (Section 17.1.2) describing methods for the synthesis of 1,4-oxazines and 1,4-benzoxazines. It includes both new methods reported in the period 2004–2013 and older methods not covered in the earlier chapter.

Keywords: 1,4-benzoxazines · nitrogen heterocycles · 1,4-oxazines · oxygen heterocycles · ring-closure reactions · substituent modification

17.1.3.9 One Sulfur, Selenium, or Tellurium Atom and One Nitrogen or Phosphorus Atom

R. A. Aitken and A. MeehanThis chapter is an update of the earlier Science of Synthesis contribution (Section 17.1.3) describing methods for the synthesis of 1,4-thiazines and 1,4-benzothiazines. In the absence of significant new methods reported in the period 2004–2013, it focuses on older methods not covered in the earlier chapter.

Keywords: 1,4-benzothiazines · nitrogen heterocycles · ring-closure reactions · substituent modification · sulfur heterocycles · 1,4-thiazines

18.2.16 Carbon Dioxide, Carbonyl Sulfide, Carbon Disulfide, Isocyanates, Isothiocyanates, Carbodiimides, and Their Selenium, Tellurium, and Phosphorus Analogues

S. Braverman and M. Cherkinsky

This chapter is an update to the earlier Science of Synthesis contribution (Section 18.2) describing methods for the synthesis and synthetic application of heterocumulenes (X=C=Y) with particular emphasis on supercritical carbon dioxide as a reaction medium for organic synthesis. It focuses on the literature published in the period 2002–2013.

Keywords: carbon dioxide · supercritical carbon dioxide · carbonyl sulfide · carbon disulfide · carbonyl selenide · isocyanates · isothiocyanates · isoselenocyanates · carbodiimides

24.2.1.3 1,1-Dihaloalk-1-enes

B. Ameduri

This chapter is an update to the earlier Science of Synthesis contribution describing methods and strategies for the synthesis of 1,1-dihaloalk-1-enes. This update focuses on the preparation and polymerization of 1,1-difluoroalk-1-enes, including trifluorovinyl functional monomers. Radical additions of chain-transfer agents onto commercially available fluoroalkenes are described, followed by their chemical modification to yield original fluorinated monomers. These monomers are further involved in radical (conventional or controlled) copolymerizations with vinylidene fluoride (1,1-difluoroethene) or chlorotrifluoroethene to achieve high-value-added materials.

Keywords: 1,1-dihaloalk-1-enes · chlorotrifluoroethene · fluoropolymers · fuel-cell membranes · NMR · radical copolymerization · trifluorovinyl functional monomers · vinylidene fluoride · 1,1-difluoroethene

24.3.12 Bis(heteroatom-functionalized) Acetylenes

J. Udmark and M. Brøndsted Nielsen

This chapter provides an update to the earlier Science of Synthesis contribution (Section 24.3) describing methods for the synthesis of bis(heteroatom-functionalized) acetylenes. Selected applications are also included. It focuses on the literature published since the original report in 2006 up until the end of 2013.

Keywords: alkynes · cross-coupling reactions · dehydrohalogenation · halogenation · nucleophilic substitution

24.4.1.3 1-Haloalk-1-ynes and Alk-1-yn-1-ols

A. U. Petersen and M. Brøndsted Nielsen

This chapter is an update to the earlier Science of Synthesis contribution (Section 24.4.1) describing methods for the synthesis of 1-haloalk-1-ynes. It focuses on the literature published since the original report in 2006 up until the end of 2013.

Keywords: alkynes · cross-coupling reactions · dehydrohalogenation · halogenation · succinimides

27.21.3 Diazo Compounds

H. Heydt

This chapter is an update to Science of Synthesis Section 27.21 and deals with the synthesis of diazo compounds and their applications in organic synthesis. The current chapter covers the literature published between 2004 and 2013. The focus of the work presented here is on new methods for the synthesis of diazoalkanes, improvement of established methods (including new variations and examples), and on some important applications of these compounds, especially relating to stereoselective synthesis.

Keywords: diazo compounds · diazotization · diazo group transfer · hydrazones · cyclopropanation · Bamford–Stevens reaction · continuous-flow methods · diazotates · diazenolates · diazoalkane substitution

39.19.2.3 Alkaneselenolates of Group 3–12 Metals

A. Polo and J. Real

This chapter is an update to the earlier Science of Synthesis contribution (Section 39.19.2) describing methods for the synthesis of transition metal selenolates and their applications in organic synthesis. Synthetic methods developed in recent years concern both terminal and bridging alkaneselenolates. New applications for this class of compounds in organic synthesis have not been proposed. However, compounds of this class have been postulated as catalytic intermediates in some reactions, such as transition-metal-catalyzed Se—C bond formation via cross-coupling reactions.

Keywords: transition metals · bridged compounds · selenium compounds · selenides · selenols · oxidative addition · cross-coupling reactions

39.26.6.2 Cyclic Alkaneselenolates of Group 3–12 Metals

A. Polo and J. Real

This chapter is an update to the earlier Science of Synthesis contribution (Section 39.26.6) describing methods for the synthesis of cyclic alkaneselenolates of transition metals and their applications in organic synthesis. Synthetic methods developed in recent years concern diselenolates, aminoselenolates, and selenolates with a metal-carbon bond. New applications for this class of compounds in organic synthesis have not been proposed.

Keywords: transition metals · bridged compounds · cyclic compounds · selenium compounds · selenides · selenols · oxidative addition · cycloaddition

39.32.2.2 Alkanetellurolates of Group 3–12 Metals

A. Polo and J. Real

This chapter is an update to the earlier Science of Synthesis contribution (Section 39.32.2) describing methods for the synthesis of transition metal alkanetellurolates and their applications in organic synthesis. Synthetic methods developed in recent years concern both terminal and bridging alkanetellurolates. New applications for this class of compounds in organic synthesis have not been proposed. However, they have been postulated as catalytic intermediates in some transition-metal-mediated cross-coupling reactions.

Keywords: transition metals · bridged compounds · tellurium compounds · tellurides · oxidative addition · cross-coupling reactions

39.39.6.2 Cyclic Alkanetellurolates of Group 3–12 Metals

A. Polo and J. Real

This chapter is an update to the earlier Science of Synthesis contribution (Section 39.39.6) describing methods for the synthesis of cyclic alkanetellurolates of transition metals and their applications in organic synthesis. Synthetic methods developed in recent years focus principally on the synthesis of ditellurolates and aminotellurolates. New applications for this class of compounds in organic synthesis have not been proposed.

Keywords: transition metals · bridged compounds · cyclic compounds · tellurium compounds · tellurides · oxidative addition

Science of Synthesis Knowledge Updates 2014/3

Preface

Abstracts

Table of Contents

10.21 Product Class 21: Five–Five-Fused Hetarenes with One Heteroatom in Each Ring

S. P. Stanforth

17.1.2.5 One Oxygen and One Nitrogen or Phosphorus Atom (Update 2014)

R. A. Aitken and A. Meehan

17.1.3.9 One Sulfur, Selenium, or Tellurium Atom and One Nitrogen or Phosphorus Atom (Update 2014)

R. A. Aitken and A. Meehan

18.2.16 Carbon Dioxide, Carbonyl Sulfide, Carbon Disulfide, Isocyanates, Isothiocyanates, Carbodiimides, and Their Selenium, Tellurium, and Phosphorus Analogues (Update 2014)

S. Braverman and M. Cherkinsky

24.2.1.3 1,1-Dihaloalk-1-enes (Update 2014)

B. Ameduri

24.3.12 Bis(heteroatom-functionalized) Acetylenes (Update 2014)

J. Udmark and M. Brøndsted Nielsen

24.4.1.3 1-Haloalk-1-ynes and Alk-1-yn-1-ols (Update 2014)

A. U. Petersen and M. Brøndsted Nielsen

27.21.3 Diazo Compounds (Update 2014)

H. Heydt

39.19.2.3 Alkaneselenolates of Group 3–12 Metals (Update 2014)

A. Polo and J. Real

39.26.6.2 Cyclic Alkaneselenolates of Group 3–12 Metals (Update 2014)

A. Polo and J. Real

39.32.2.2 Alkanetellurolates of Group 3–12 Metals (Update 2014)

A. Polo and J. Real

39.39.6.2 Cyclic Alkanetellurolates of Group 3–12 Metals (Update 2014)

A. Polo and J. Real

Author Index

Abbreviations

Table of Contents

Volume 10: Fused Five-Membered Hetarenes with One Heteroatom

10.21 Product Class 21: Five–Five-Fused Hetarenes with One Heteroatom in Each Ring

S. P. Stanforth

10.21 Product Class 21: Five–Five-Fused Hetarenes with One Heteroatom in Each Ring

10.21.1 Product Subclass 1: Hetaryl[3,2-b]hetarenes (1,4-Diheteropentalenes)

10.21.1.1 Synthesis by Ring-Closure Reactions

10.21.1.1.1 By Annulation to a Hetarene

10.21.1.1.1.1 By Formation of Two Heteroatom—Carbon Bonds

10.21.1.1.1.1.1 Method 1: Synthesis from Alkynyldiols

10.21.1.1.1.1.2 Method 2: Synthesis from 2-Alkynyl-3-bromohetarenes

10.21.1.1.1.1.3 Method 3: Synthesis from 3-Bromo-2-(2-bromoalkenyl)hetarenes

10.21.1.1.1.2 By Formation of One Heteroatom—Carbon Bond and One C-C Bond

10.21.1.1.1.2.1 Method 1: Synthesis from 2-Acetyl-3-halothiophenes

10.21.1.1.1.3 By Formation of One Heteroatom—Carbon Bond

10.21.1.1.1.3.1 Method 1: Formation of a Ring-Junction Heteroatom—Carbon Bond

10.21.1.1.1.3.1.1 Variation 1: From 2-(2-Sulfanylalkenyl)hetarenes

10.21.1.1.1.3.1.2 Variation 2: From 2-(2-Azidoalkenyl)hetarenes

10.21.1.1.1.3.2 Method 2: Formation of a Non-Ring-Junction Heteroatom—Carbon Bond

10.21.1.1.1.3.2.1 Variation 1: From 2-Alkynyl-3-(tert-butylsulfanyl)hetarenes

10.21.1.1.1.3.2.2 Variation 2: From 2-Alkynyl-3-aminohetarenes

10.21.1.1.1.3.2.3 Variation 3: From 2-Alkenyl-3-nitrohetarenes and Related Compounds

10.21.1.1.1.3.2.4 Variation 4: From 2-Alkenyl-3-azidohetarenes

10.21.1.1.1.3.2.5 Variation 5: From 3-Amino-2-(2,2-dichlorovinyl)hetarenes

10.21.1.1.1.3.2.6 Variation 6: From 3-Hydroxy-2-(2-oxoalkyl)hetarenes

10.21.1.1.1.4 By Formation of One C—C Bond

10.21.1.1.1.4.1 Method 1: Formation of a C—C Bond between Two Non-Ring-Junction Carbons

10.21.1.1.1.4.2 Method 2: Formation of a C—C Bond between One Ring-Junction Carbon and One Non-Ring-Junction Carbon

10.21.1.1.1.4.2.1 Variation 1: By a Cyclodehydrationor Equivalent Reaction

10.21.1.1.1.4.2.2 Variation 2: By a Dehydrohalogenation Reaction

10.21.1.1.1.4.2.3 Variation 3: By an Oxidative Cyclization Reaction

10.21.1.2 Synthesis by Ring Transformation

10.21.1.2.1 Method 1: Ring Contraction of 1λ4,2-Thiazine

10.21.1.3 Aromatization

10.21.1.3.1 Method 1: Dehydrogenation

10.21.1.3.2 Method 2: Dehydration

10.21.1.4 Synthesis by Substituent Modification

10.21.1.4.1 Substitution of Existing Substituents

10.21.1.4.1.1 Of C-Hydrogen

10.21.1.4.1.1.1 Method 1: Formation of C-Metal Compounds

10.21.1.4.1.1.1.1 Variation 1: Formation of C-Lithium

10.21.1.4.1.1.1.2 Variation 2: Formation of C-Magnesium

10.21.1.4.1.1.2 Method 2: Formation of C-Carbon Compounds

10.21.1.4.1.1.2.1 Variation 1: Formation of C-Nitrile

10.21.1.4.1.1.2.2 Variation 2: Formation of C-Alkene

10.21.1.4.1.1.2.3 Variation 3: Formation of C-Carbonyl

10.21.1.4.1.1.2.4 Variation 4: Formation of C-(Aminoalkyl)

10.21.1.4.1.1.2.5 Variation 5: Oxidative Coupling Giving Hetarene Polymers

10.21.1.4.1.1.3 Method 3: Formation of C-Halogen Compounds

10.21.1.4.1.1.4 Method 4: Formation of C-Nitrogen Compounds

10.21.1.4.1.2 Of N-Hydrogen

10.21.1.4.1.2.1 Method 1: N-Alkylation

10.21.1.4.1.3 Of Metals

10.21.1.4.1.3.1 Method 1: Formation of C-Hydrogen Compounds

10.21.1.4.1.3.2 Method 2: Formation of Different C-Metal Compounds

10.21.1.4.1.3.2.1 Variation 1: Formation of C-Boron

10.21.1.4.1.3.2.2 Variation 2: Formation of C-Silicon

10.21.1.4.1.3.2.3 Variation 3: Formation of C-Tin

10.21.1.4.1.3.3 Method 3: Formation of C-Carbon Compounds

10.21.1.4.1.3.3.1 Variation 1: Formation of C-Carboxylic Acid and C-Ester

10.21.1.4.1.3.3.2 Variation 2: Formation of C-Carbonyl

10.21.1.4.1.3.3.3 Variation 3: Formation of C-(1-Hydroxyalkyl)

10.21.1.4.1.3.3.4 Variation 4: Formation of C-Alkyl

10.21.1.4.1.3.3.5 Variation 5: Reductive Elimination Giving Hetarene Oligomers

10.21.1.4.1.3.3.6 Variation 6: Formation of C-Aryl:Suzuki–Miyaura Reaction

10.21.1.4.1.3.3.7 Variation 7: Formation of C-Aryl: Stille Reaction

10.21.1.4.1.3.4 Method 4: Formation of C-Heteroatom Compounds

10.21.1.4.1.3.4.1 Variation 1: Formation of C-Halogen

10.21.1.4.1.3.4.2 Variation 2: Formation of C-Oxygen: Oxidation of Boronic Acids

10.21.1.4.1.3.4.3 Variation 3: Formation of C-Sulfur, C-Selenium, or C-Tellurium

10.21.1.4.1.4 Of Carbon Functionalities

10.21.1.4.1.4.1 Of C-Carboxylic Acid

10.21.1.4.1.4.1.1 Method 1: Formation of C-Hydrogen Compounds

10.21.1.4.1.4.1.2 Method 2: Formation of C-Aldehydes

10.21.1.4.1.4.1.3 Method 3: Formation of C-Bromides

10.21.1.4.1.5 Of Heteroatoms

10.21.1.4.1.5.1 Of C-Halogen

10.21.1.4.1.5.1.1 Method 1: Formation of C-Hydrogen Compounds

10.21.1.4.1.5.1.2 Method 2: Formation of C-Metal Compounds

10.21.1.4.1.5.1.3 Method 3: Formation of C-Alkyl Compounds

10.21.1.4.1.5.1.4 Method 4: Formation of C-Aryl Compounds: Suzuki–Miyaura Reaction

10.21.1.4.1.5.1.5 Method 5: Formation of C-Aryl Compounds: Stille Reaction

10.21.1.4.1.5.1.6 Method 6: Formation of C-Heteroatom Compounds

10.21.1.4.2 Addition Reactions

10.21.1.4.2.1 Addition of Heteroatoms

10.21.1.4.2.1.1 Method 1: Synthesis of S,S-Dioxides

10.21.1.4.3 Rearrangement of Substituents

10.21.1.4.3.1 Method 1: “Halogen Dance” Isomerization

10.21.1.4.4 Modification of Substituents

10.21.1.4.4.1 Method 1: O-Alkylation

10.21.2 Product Subclass 2: Hetaryl[2,3-c]hetarenes and Hetaryl[3,4-b]hetarenes (1,5-Diheteropentalenes)

10.21.2.1 Synthesis by Ring-Closure Reactions

10.21.2.1.1 By Annulation to a Hetarene

10.21.2.1.1.1 By Formation of Two Heteroatom—Carbon Bonds

10.21.2.1.1.1.1 Method 1: Synthesis from 4-Oxoprolines

10.21.2.1.1.1.2 Method 2: Synthesis from 2(3)-Acetylthiophene-3(2)-carbaldehydes

10.21.2.1.1.1.3 Method 3: Synthesis from 2-[Hydroxy(aryl)methyl]thiophene-3-carbaldehydes

10.21.2.1.1.1.4 Method 4: Synthesis from 3-Aroyl-2-(bromomethyl)hetarenes

10.21.2.1.1.1.5 Method 5: Synthesis from 4-Bromo-3-(2-bromoalkenyl)hetarenes

10.21.2.1.1.1.6 Method 6: Synthesis from 2-{[2(3)-(Bromomethyl)-3(2)-hetaryl]methylene]malonates

10.21.2.1.1.2 By Formation of One Heteroatom—Carbon and One C—C Bond

10.21.2.1.1.2.1 Method 1: Synthesis from 2-Thioaroylhetarenes

10.21.2.1.1.3 By Formation of One Heteroatom—Carbon Bond

10.21.2.1.1.3.1 Method 1: Synthesis from 2-Alkynyl-3-bromohetarenes

10.21.2.1.1.3.2 Method 2: Synthesis from 2-{[2(3)-(Azidomethyl)-3(2)-hetaryl]methylene]malonates

10.21.2.1.1.3.3 Method 3: Synthesis from 2-Benzoyl-3-[(ethylsulfinyl)methyl]thiophene and Related Compounds