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Synthesis 2008(13): 2105-2109  
DOI: 10.1055/s-2008-1067120
PAPER
© Georg Thieme Verlag Stuttgart · New York

Formal Synthesis of (-)-Frontalin through Diastereoselective Hydrocyanation of a β-Keto Sulfoxide

Benjamín Ortiz, Rubén Sánchez-Obregón, Rubén A. Toscano, Francisco Yuste*
Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Cd. Universitaria, Coyoacán 04510 México, D. F., Mexico
Fax: +52(55)56162217; e-Mail: yustef@servidor.unam.mx;
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Publication History

Received 7 February 2008
Publication Date:
11 June 2008 (online)

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Abstract

The diastereoselective synthesis of (S)-4-(2,2,4-trimethyl-1,3-dioxolan-4-yl)butan-1-ol (9), an intermediate in the asymmetric synthesis of the pine beetle pheromone (-)-frontalin [(1S,5R)-1,5-dimethyl-6,8-dioxabicyclo[3.2.1]octane] (1), has been accomplished starting from the β-keto sulfoxide 2, derived from glutaric anhydride. The key step of the synthetic sequence is the diastereoselective hydrocyanation of 2 by diethylaluminum cyanide.

Key words

asymmetric synthesis - frontalin - diastereoselective hydrocyanation - chiral cyanohydrins - β-keto sulfoxides

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Supplementary crystallographic data for 4 and 5 have been deposited with the Cambridge Crystallographic Data Centre as publication numbers 4: CCDC 666954 and 5: CCDC 666955. Copies of the data may be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: +44 1223 33603 or via www.ccdc.cam.ac.uk/data_request/cif).