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Synlett 2006(10): 1527-1530  
DOI: 10.1055/s-2006-941599
LETTER
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Synthesis of Bicyclo[4.4.1]undecane-2,7-dione via ­Samarium(II)-Mediated Fragmentation of a Cyclopropane Precursor

Sherif El Sheikh, Nina Kausch, J. Lex, J.-M. Neudörfl, Hans-Günther Schmalz*
Institut für Organische Chemie, Universität zu Köln, Greinstr. 4, 50939 Köln, Germany
Fax: +49(221)4703064; e-Mail: schmalz@uni-koeln.de;
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Publication History

Received 4 April 2006
Publication Date:
12 June 2006 (online)

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Abstract

An efficient six-step synthesis of bicyclo[4.4.1]undecane-2,7-dione was elaborated. Key steps include an enantioselective oxazaborolidine-catalyzed borane reduction (CBS reduction) of 2,3,4,6,7,8-hexahydronaphthalene-1,5-dione to the corresponding diol, and a subsequent (syn-diastereoselective) cyclopropanation. Oxidation then gives tricyclo[4.4.1.01,6]undecane-2,7-dione (>99% ee) which on treatment with two equivalents of samarium(II) iodide undergoes cleavage of the central cyclopropane bond to yield the target compound without any loss of stereochemical information.

Key words

asymmetric synthesis - chirality - cyclopropane - fragmentation - samarium diiodide

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