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Diastereospecific carbonylation of π-allylpalladium complexes to give 3,6-disubstituted 3,6-dihydro-1H-pyridin-2-ones

Lookup NU author(s): Dr Julian Knight, Dr Kirill Tchabanenko

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Abstract

(Ph3P)2PdCl2 was found to be the most effective of a range of catalysts for decarboxylative carbonylation of (4S,5RS)-5-ethenyl-4-(2-propyl)oxazolidin-2-one to give the δ-lactam, (6S)-3,6-dihydro-6-(2-propyl)-1H-pyridin-2-one. In a similar way, diastereoisomerically pure (4S,5S)-4-benzyl-5-((Z)alk-1-enyl)oxazolidin-2-ones undergo stereospecific carbonylation to give (3R,6S)-6-benzyl-3-alkyl-3,6-dihydro-1H-pyridin-2-ones. The diastereoisomeric (4S,5R)-4-benzyl-5-((Z)alk-1-enyl)oxazolidin-2-ones give rise to a separable mixture of the corresponding (3S,6S)-6-benzyl-3-alkyl-3,6-dihydro-1H-pyridin-2-one and (4S,5S)-4-benzyl-5-((E)alk-1-enyl)oxazolidin-2-one. Under more forcing conditions, the latter oxazolidinone is carbonylated to the 3,6-anti-pyridinone. The stereochemical course of the reactions can be rationalized by formation of a π-allyl palladium cation with inversion of configuration followed by carbonylation with retention. The stereospecificity observed in our system precludes metal-metal exchange of the π-allyl complexes by a Pd(0) displacement process. © 2002 Elsevier Science Ltd. All rights reserved.


Publication metadata

Author(s): Knight JG, Tchabanenko K

Publication type: Article

Publication status: Published

Journal: Tetrahedron

Year: 2002

Volume: 58

Issue: 33

Pages: 6659-6664

Print publication date: 12/08/2002

ISSN (print): 0040-4020

ISSN (electronic): 1464-5416

URL: http://dx.doi.org/10.1016/S0040-4020(02)00683-X

DOI: 10.1016/S0040-4020(02)00683-X


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