General and Synthetic Methods: Volume 3 (Specialist Periodical Reports, Band 3) - Hardcover

Hardcover

ISBN 10: 0851867308 ISBN 13: 9780851867304

Verlag: Royal Society of Chemistry, 1980

Inhaltsangabe

Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.

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A series of reviews by leading specialists in their fields which gives systematic and comprehensive coverage of the progress in major areas of research.

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General and Synthetic Methods Volume 3

A Review of the Literature Published During 1978

By G. Pattenden

The Royal Society of Chemistry

Copyright © 1980 The Chemical Society
All rights reserved.

ISBN: 978-0-85186-730-4

Contents

Chapter 1 Saturated and Unsaturated Acyclic Hydrocarbons By D. C. Harwell, 1, 
Chapter 2 Aldehydes and Ketones By S. M. Roberts, 36, 
Chapter 3 Carboxylic Acids and Derivatives By D. W. Knight, 75, 
Chapter 4 Alcohols, Halogeno-compounds, and Ethers By R. C. F. Jones, 132, 
Chapter 5 Amines, Nitriles, and Other Nitrogen-containing Functional Groups By G. Kneen, 164, 
Chapter 6 Organometallics in Synthesis Part I The Transition Elements By D. J. Thompson, 183, 
Chapter 7 Saturated Carbocyclic Ring Synthesis By K. Cooper, M. Mellor, and G. Pattenden, 227, 
Chapter 8 Saturated Heterocyclic Ring Synthesis By W. J. Ross, 265, 
Chapter 9 Strategy and Design in Synthesis By S. J. Turner, 312, 
Chapter 10 Photochemistry in Synthesis By A. B. Holmes, 329, 
Author Index, 365, 

CHAPTER 1

Saturated and Unsaturated Acyclic Hydrocarbons

BY D. C. HORWELL

1 Introduction

Volume 1 of the much heralded treatise 'Comprehensive Organic Chemistry' has now appeared, and has three chapters devoted to saturated hydrocarbons, olefinic hydrocarbons, dienes, polyenes, and acetylenic hydrocarbons. Two reviews summarize olefin synthesis via β-functionalized organosilicon compounds, with discussion of stereochemical control vis à vis the Wittig reaction. Clive has surveyed modern organoselenium chemistry, including the conversion of epoxides into olefins, inversion of olefinic geometry, selenoxide fragmentation, and the conversion of β-hydroxyalkyl selenides into allylic alcohols and olefins. Selective reactions with diethylaluminium–2,2,6,6-tetramethylpiperidine, including stereo- and regio-selective isomerizations of substituted epoxides into allylic alcohols and their further regiospecific transformation into 1,3-dienes, are discussed. Warren has reviewed the use of migrating Ph2PO and PhS groups in the synthesis of 1,3-dienes and allylic alcohols and modern routes to interesting sterically crowded olefins are summarized by Tidwell. Selective eliminations on alumina surfaces to give olefins are reviewed by Posner, whilst Oppolzer and Snieckus have discussed the use of the intramolecular 'ene' reaction in organic synthesis. A detailed review on the use of alkenyl-, alkynyl-, and cyanoborates as synthetic intermediates to alkynes, diynes, and enynes, and their stereochemical control of di-, tri- and tetra-substituted olefin synthesis, has appeared. Olefin photochemistry is analysed in terms of the rearrangements and fragmentations that may occur, and some such reactions are illustrated by the industrial synthesis of Vitamin D. Stang has reviewed the generation of unsaturated carbenes and their addition to other unsaturated moieties to give cumulenes and acetylenes. Further chemistry of poly-unsaturated hydrocarbons is included in a review on the synthesis of the chiral component of insect pheromones, and applications of the retro-Diels–Alder reaction in organic synthesis have been summarized.

2 Saturated Hydrocarbons

Alternative procedures to catalytic hydrogenation for the reduction of olefins to alkanes have appeared this year. A particularly smooth procedure has been the utilization of sodium hydrogen telluride as illustrated in Scheme 1. Ashby and co-workers have studied the reduction of olefins with bis-d1-iso-propylaminoalane, and with magnesium hydride, both catalysed with [Cp2TiCl2]. Lithium aluminium hydride-transition-metal mixtures also reduce olefins and halides, with catalytic amounts of CoCl2 and NiCl2 particularly effective. Itaconic acid is hydrogenated asymmetrically in 83.5% (S) optical yield by benzoyl (2S, 4S)-4-diphenylphosphino-2-diphenylphosphinomethyl-pyrrolidine, and hydrogen transfer with cyclohexene-Pd-C-A1Cl3 has been shown to be effective in hydrogenating both aryl olefins and aryl alcohols to aylalkanes.

Selective reductive removal of functional groups as a synthetic route to alkanes has been further developed this year. Two research groups report new mild procedures for the reduction of esters and sterically hindered alcohols to the corresponding alkanes in good yield, and without any rearrangement. Thus, tertiary steroidal acetates are reduced by Li–EtNH2 or K–ButNH2–18- crown- 6, and methane sulphonate esters by lithium triethylborohydride (Scheme 2). Sodium in HMPA is also an effective new reagent for both the reduction of esters and the deoxygenation of alcohols to give alkanes. Deoxygenation of ketones and primary alcohols may be achieved under mild conditions in good to excellent yield, by reduction of their phenylselenoacetals and selenides respectively, with triphenyltin hydride; the selenoacetals are readily prepared from the aldehyde or ketone using the easily available crystalline reagent tris(phenylseleno)borane, in the presence of TFA. In addition to this procedure, aldehydes and ketones are deoxygenated directly in good yield with triethylsilane in the presence of gaseous boron trifluoride, and thioketones are readily desulphurized by four equivalents of [HFe(CO)4]-. Kornblum and his co-workers have described a highly efficient method for the replacement of a nitro-group by hydrogen, on treatment with the sodium salt of methyl mercaptan in an aprotic dipolar solvent at room temperature. The reduction probably proceeds via a radical anion process, and can tolerate the presence of other functionality, such as the cyano-, keto-, and ester groups (Scheme 3).

The photocatalytic decarboxylation of saturated carboxylic acids to alkanes has been shown to occur on TiO2 powder. The direct replacement of primary aliphatic amino-groups for hydrogen, termed 'hydrodeamination', takes place readily under mild conditions, on treatment with hydroxylamine-O-sulphonic acid and sodium hydroxide;33 the reaction works well even on amino-acid and dipeptide substrates. Aliphatic amines may also be used to introduce the triftuoromethyl group directly, by the novel procedure outlined in Scheme 4.

3 Olefinic Hydrocarbons

Several factors which influence the rate and yield of the 'ene' reaction have been identified this year. Gladysz and Yu have found that the thermal ene reaction of β-pinene, which otherwise occurs only at temperatures greater than 150 °C, proceeds readily at room temperature under 40 kbar pressure (39 500 atm). For example, methyl pyruvate and β-pinene have been reported to react at 165 °C to afford the adduct (1) in 55% yield. Since (1) undergoes a rapid retro-ene reaction at this temperature, this yield is believed to represent the maximum equilibrium yield attainable. However, (1) is formed in quantitative yield at room temperature at 40 kbar pressure!

The intramolecular ene reaction of the 1,6-enyne (2) appears to be retarded by a terminal methyl substituent, but significantly accelerated by an electron-withdrawing substituent, such as the methoxycarbonyl group. These observations are pertinent to the conversion (2) -> (3) in a synthetic strategy to the iridoid carbon skeleton.

The eutectic mixture AlCl3–NaCl–KCl has been found to be a superior catalyst to A1Cl3 alone, in the Lewis acid-catalysed ene reaction of methyl acrylate with terminal olefins. Hence an 86 : 14 mixture of geometrical isomers of (4) is obtained from...

Details zur Ausgabe

• Verlag: Royal Society of Chemistry
• Erscheinungsdatum: 1980
• Sprache: Englisch
• ISBN 10: 0851867308
• ISBN 13: 9780851867304
• Einband: Gebundene Ausgabe
• Anzahl der Seiten: 400
• Herausgeber: Pattenden G.
• Kontakt zum Hersteller: Nicht verfügbar
• Verantwortliche Person: GPSR Kontakt; gpsr@libri.de; ; Europaallee 1; Bad Hersfeld; 36244; Deutschland