Modern Synthetic Methods 1986 : Conference Papers of the International Seminar on Modern Synthetic Methods 1986, Interlaken, April 17th/18th 1986

R. Scheffold

ISBN 10: 3540165266 / ISBN 13: 9783540165262

Editore: Springer, Springer Vieweg, 1986

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Druck auf Anfrage Neuware - Printed after ordering - 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 .,.

Codice articolo 9783540165262

Dati bibliografici

• Titolo: Modern Synthetic Methods 1986 : Conference Papers of the International Seminar on Modern Synthetic Methods 1986, Interlaken, April 17th/18th 1986
• Editore: Springer, Springer Vieweg
• Data di pubblicazione: 1986
• Lingua: Inglese
• ISBN 10: 3540165266
• ISBN 13: 9783540165262
• Rilegatura: Taschenbuch
• Condizione: Neu
• Dimensioni: 210 L x 148 A x 20 P (millimetri) 210 millimetri di larghezza per 148 millimetri di altezza per 20 millimetri di profondità
• Peso: 476 grammi

Descrizione articolo

Riassunto

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 .,.

Contenuti

Sound and Light in Synthesis.- Ultrasound in Synthesis.- Photochemically Generated Building Blocks I.- Photochemically Generated Building Blocks II The Tricyclooctanone Approach.- Synthesis of Enantiomerically Pure Compunds with C,C Bond Formation.- EPC Syntheses with C,C Bond Formation via Acetals and Enamines.- Asymmetric Diels-Alder Reactions with Chiral Enoates as Dienophiles.- Enantiomerically Pure Compounds via Chiral Organoboranes.