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Article << Previous     |     Next >>   Contents Vol 67(9)

Facial Selectivity in the Addition of Lithium Dimethylcuprate to 6-Substituted Tricyclo[,6]deca-4,8-dienones. Synthesis of β-Substituted Cyclopentenones Using Flash Vacuum Thermolysis

Antonius J. H. Klunder A , Andries A. Volkers A and Binne Zwanenburg A B

A Radboud University Nijmegen, Institute for Molecules and Materials, Department of Organic Chemistry, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
B Corresponding author. Email: B.Zwanenburg@science.ru.nl

Australian Journal of Chemistry 67(9) 1243-1250 http://dx.doi.org/10.1071/CH14094
Submitted: 25 February 2014  Accepted: 6 April 2014   Published: 29 April 2014

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The stereoselectivity of the nucleophilic addition of lithium dimethylcuprate and lithium di-n-pentylcuprate to 6-substituted tricyclo[,6]deca-4,8-dienones was investigated. It was shown that substituents at the 6-position can either exert a steric effect or an electronic effect. Steric approach control predominantly giving the endo product was observed for 6-alkyl substituents. Stereoelectronic control could be adequately rationalised using the Cieplak model. Flash vacuum thermolysis was used to prepare a series of β-substituted cyclopentenoids. The sequence leading to cyclopentenoids has an attractive scope.


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