Modern Synthetic Methods 1986

R. Scheffold

ISBN 10: 3540165266 / ISBN 13: 9783540165262

Published by Springer Berlin Heidelberg, Springer Berlin Heidelberg Apr 1986, 1986

About this Item

This item is printed on demand - it takes 3-4 days longer - Neuware -In the tricyclooctanone approach to polyquinane syntheses[ll the photochemical rearrangement of bicyclo[2.2.2]octenone, 1a 2a,[2J has been the initial key reaction providing tricyclo 2 [3.3.0.0 ' S]octan-3-one as a chiral building block.[3-SJ This reaction - an oxadi-n-methane (ODPM) process - and the 1,3-acyl shift (AS) forming the cyclobutanone 3 are quite generally the characteristic re arrangement paths undergone by ~,~-unsaturated ketones (~,~-UKs) upon triplet sensitization and direct excitation with ultraviolet light, respectively. R' R' hv hv R~O ~ ~ (sens) WO ~ R ONR R 1a-c 2a-c 3a-c a R=R'=H b R = CH , R'= H 3 c R = R'= CH 3 As a polyvalent building block, the enantiomers of which are readily accessible from cheap bulk chemicals such as benzene and its derivatives, the parent system 1a and three younger generations of its class (Sections 3.1. - 3.4.) have no equal among synthetically useful photochemical rearrangements. 2. THE PHOTOCHEMISTRY OF ~,~-UNSATURATED KETONES The literature dealing with the spectroscopy and photo chemistry of ~,~-UKs has been exhaustively and critically reviewed around 1975 by Dauben et al.[6l and Houk,[7J and in 1980 by Schuster.[SlI1 The 1,3-AS was first observed on direct excitation of 1) For more recent papers on i3,~-UK photochemistry see [9-24]. 64 ~ R' hv ~o hv ., 368 pp. Englisch.

Seller Inventory # 9783540165262

Bibliographic Details

• Title: Modern Synthetic Methods 1986
• Publisher: Springer Berlin Heidelberg, Springer Berlin Heidelberg Apr 1986
• Publication Date: 1986
• Language: English
• ISBN 10: 3540165266
• ISBN 13: 9783540165262
• Binding: Taschenbuch
• Condition: Neu
• Dimensions: 210W x 148H x 20D millimeters 210 millimeters width by 148 millimeters height by 20 millimeters depth
• Weight: 476 grams

About this title

Synopsis

In the tricyclooctanone approach to polyquinane syntheses[ll the photochemical rearrangement of bicyclo[2.2.2]octenone, 1a 2a, [2J has been the initial key reaction providing tricyclo- 2 [3.3.0.0 ' S]octan-3-one as a chiral building block.[3-SJ This reaction - an oxadi-n-methane (ODPM) process - and the 1,3-acyl shift (AS) forming the cyclobutanone 3 are quite generally the characteristic re- arrangement paths undergone by, -unsaturated ketones (, -UKs) upon triplet sensitization and direct excitation with ultraviolet light, respectively. R' R' hv hv R O (sens) WO R ONR R 1a-c 2a-c 3a-c a R=R'=H b R = CH, R'= H 3 c R = R'= CH 3 As a polyvalent building block, the enantiomers of which are readily accessible from cheap bulk chemicals such as benzene and its derivatives, the parent system 1a and three younger generations of its class (Sections 3.1. - 3.4.) have no equal among synthetically useful photochemical rearrangements. 2. THE PHOTOCHEMISTRY OF, -UNSATURATED KETONES The literature dealing with the spectroscopy and photo- chemistry of, -UKs has been exhaustively and critically reviewed around 1975 by Dauben et al.[6l and Houk, [7J and in 1980 by Schuster.[SlI1 The 1,3-AS was first observed on direct excitation of 1) For more recent papers on i3, -UK photochemistry see [9-24]. 64 R' hv o hv ., .