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Synlett 2008(14): 2155-2157  
DOI: 10.1055/s-2008-1077902
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Semi-Pinacol Rearrangement Approach to Bicyclo[3.2.1]octan-2-ones and Bicyclo[3.2.1]octan-3-ones

Sejin Lee, Keunho Kim, Jin Kun Cha*
Department of Chemistry, Wayne State University, 5101 Cass Ave, Detroit, MI 48202, USA
Fax: +1(313)5778822; e-Mail: jcha@chem.wayne.edu;
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Publikationsverlauf

Received 9 May 2008
Publikationsdatum:
02. Juli 2008 (online)

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Abstract

A diastereoselective approach to bicyclo[3.2.1]octan-2-ones and -3-ones is achieved by means of the semi-pinacol rearrangement of 2,3-epoxy silyl ethers. The key 1,2-migration is stereospecific. This method is easily amenable to an enantioselective synthesis by utilizing nonracemic norcamphor and related compounds.

Key words

rearrangement - ring expansion - epoxides - stereoselectivity

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14

Tin(IV) chloride had successfully been employed for a stereoselective, semipinacol rearrangement of 2,3-epoxy alcohols without protection of alcohols.7a

15

As 12 was found to be somewhat labile toward acid (e.g., SiO2), it was isolated as the corresponding E-enone.