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Intramolecular Cyclopropanation of Unsaturated Terminal Epoxides and Chlorohydrins

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David M. Hodgson,*^† Ying Kit Chung,^† Irene Nuzzo,^† Glòria Freixas,^† Krystyna K. Kulikiewicz,^† Ed Cleator,^‡ and Jean-Marc Paris^§

Contribution from the Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, U.K., Department of Process Research, Merck Sharp and Dohme Limited, Hertford Road, Hoddesdon, Hertfordshire, EN11 9BU, U.K., and Rhodia Recherches, Centre de Recherches de Lyon, 85 Avenue des Frères Perret, 69192 Saint Fons, France

J. Am. Chem. Soc., 2007, 129 (14), pp 4456–4462

DOI: 10.1021/ja0672932

Publication Date (Web): March 21, 2007

Section:

Terpenes and Terpenoids

Abstract

Lithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo[3.1.0]hexan-2-ols via Sn−Li exchange/electrophile trapping or Stille coupling generates a range of substituted bicyclic cyclopropanes. An alternative straightforward cyclopropanation protocol using a catalytic amount of 2,2,6,6-tetramethylpiperidine (TMP) allows for a convenient (1 g−7.5 kg) synthesis of bicyclo[3.1.0]hexan-2-ol and other bicyclic adducts. The synthetic utility of this chemistry has been demonstrated in a concise asymmetric synthesis of (+)-β-cuparenone. The related unsaturated chlorohydrins also undergo intramolecular cyclopropanation via in situ epoxide formation.

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