Beschreibung
Very few fields in science have shown. such an acceleration from theory to practice as the field of asymIfletric synthesis. When one considers that the phrase 'asymmetric synthesis' was just a mechanistic curiosity in 1965 with no one seriously believing that this could someday be an important part of molecular synthesis, the rate of progress has been quite remarkable. In just over twenty years the organic chemist has transformed this virtually unknown aspect of synthesis into a serious route to virtually every class of chiral organic compounds in greater than 90% enantiomeric purity. It is presently still enjoying significant growth and our understanding of many of the guiding principles makes it necessary to introduce the subject to students at a stage just after the initial introduction to traditional organic chemistry. It can now be safely stated that asymmetric synthesis may take its place among other, more traditional, methods for reaching enantiomeri cally pure compounds (resolution, microbiological processes, enzyme catalyzed reactions). This monograph does an admirable job of bringing all the aspects of stereochemical principles and their application to a variety of asymmetric processes, to the young student of organic chemistry. Although not exhaustive in its coverage, it lays out the foundation in excellent form, with sufficient examples, so that the student can gain an appreciation of the progress made to date.
Autorenporträt
Inhaltsangabe1 Chirality.- 1.1 The phenomenon of chirality.- 1.2 The biological significance of chirality: the need for asymmetric synthesis.- 1.3 The selective synthesis of enantiomers.- 1.4 The enantiomeric purity of natural products.- 1.5 The stereogenic unit and types of chiral compound.- 1.6 Centrally chiral compounds of carbon and silicon.- 1.7 Centrally chiral compounds of nitrogen and phosphorus.- 1.8 Centrally chiral compounds of sulphur.- 1.9 Axially chiral compounds.- 1.10 Chiral molecules with more than one stereogenic unit: diastereomers.- 1.11 The selective synthesis of diastereomers.- 1.12 Prochirality: enantotopic and diastereotopic groups.- 1.13 Absolute configuration 20 Reference and notes.- 2 The description of stereochemistry.- 2.1 Compounds with one stereogenic centre.- 2.2 Axially chiral compounds.- 2.3 Compounds with more than one stereogenic unit.- 2.4 The topicity of enantioselective reactions.- 2.5 The relative topicity of diastereoselective reactions.- 2.6 Further points on correct terminology.- References and notes.- 3 Analytical methods: determination of enantiomeric purity.- 3.1 Polarimetric methods.- 3.2 Gas chromatography methods.- 3.3 Liquid Chromatographic methods.- 3.4 NMR spectroscopy.- 3.4.1 Chiral derivatising agents (CDAs).- 3.4.2 Chiral solvating agents (CSAs).- 3.4.3 Chiral lanthanide shift reagents (CLSRs).- 3.5 Concluding remarks.- References and notes.- 4 Sources and strategies for the formation of chiral compounds.- 4.1 Chiral starting materials.- 4.1.1 Amino acids and amino alcohols.- 4.1.2 Hydroxy acids.- 4.1.3 Alkaloids and other amines.- 4.1.4 Terpenes.- 4.1.5 Carbohydrates.- 4.2 Methods for the formation of chiral compounds.- 4.2.1 Use of naturally occurring chiral compounds as building blocks.- 4.2.2 Resolution.- 4.2.3 Methods of asymmetric synthesis.- 4.2.4 Special methods.- 4.3 Mechanistic considerations.- References and notes.- 5 First- and second-generation methods: chiral starting materials and auxiliaries.- 5.1 Non-stereodifferentiating methods.- 5.1.1 Classical resolution ((lR)-cis -permethric acid).- 5.1.2 Resolution using a chiral auxiliary.- 5.1.3 Sulphoximines.- 5.1.4 Methods using enantiomerically pure building blocks.- 5.2 First-generation methods.- 5.2.1 Sugars.- 5.2.2 Amino acids.- 5.2.3 Terpenoids.- 5.2.4 Hydroxy acids.- 5.3 Second-generation methods: nucleophiles bearing a chiral auxiliary.- 5.3.1 General principles.- 5.3.2 Chiral enolate and aza-enolate equivalents.- 5.3.3 Asymmetric aldol reactions.- 5.3.4 Asymmetric ?-amino anions.- 5.3.5 Chiral sulphoxides.- 5.4 Electrophiles bearing chiral auxiliaries.- 5.4.1 Asymmetric Michael additions.- 5.4.2 Chiral acetals.- 5.4.3 Asymmetric additions to carbonyl compounds.- 5.5 Chiral auxiliaries in concerted reactions.- 5.5.1 Diels-Alder cycloaddition.- 5.5.2 The Claisen-Cope rearrangement.- References.- 6 Third- and fourth-generation methods: asymmetric reagents and catalysts.- 6.1 C-C bond-forming reactions.- 6.1.1 Asymmetric alkylation.- 6.1.2 Asymmetric Michael reaction.- 6.1.3 Asymmetric nucleophilic additions to carbonyl compounds.- 6.1.4 Asymmetric [2 + 2] cycloadditions.- 6.1.5 Asymmetric Diels-Alder reaction.- 6.1.6 Crotylboranes.- 6.1.7 Asymmetric formation of alkene double bonds.- 6.2 Chiral acids and bases.- 6.3 Asymmetric oxidation methods.- 6.3.1 Asymmetric epoxidation of alkenes.- 6.3.2 Asymmetric oxidation of sulphides.- 6.3.3 Asymmetric dihydroxylation.- 6.3.4 Chiral oxaziridines and their uses.- 6.4 Asymmetric reduction, double bond isomerisation and hydroboration.- 6.4.1 Catalytic hydrogenation with chiral transition metal complexes.- 6.4.2 Asymmetric double bond isomerisation.- 6.4.3 Asymmetric hydroboration of alkenes.- 6.4.4 Asymmetric reduction using chiral boranes and borohydrides.- 6.4.5 Chirally modified LiAlH4.- 6.5 Enzymatic and microbial methods.- 6.5.1 Enzymatic reduction.- 6.5.2 Enantioselective microbial oxidations.- 6.5.3 Esterases and lipases.- References.- 7 Asymmetric total synthesis.- 7.1 Fir
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