Diastereocontrol in the Synthesis of Models of Rings C and D of Phorbol: Directing Effect of an Ether Substituent on Lithium Carbenoid Mediated Cyclopropanation

Michael G B Drew; Laurence M Harwood; Antonio J Macías-Sánchez; Richard Scott; R M Thomas; Daniel Uguen

doi:10.1002/1521-3773(20010618)40:12<2311::AID-ANIE2311>3.0.CO;2-T

Diastereocontrol in the Synthesis of Models of Rings C and D of Phorbol: Directing Effect of an Ether Substituent on Lithium Carbenoid Mediated Cyclopropanation

Angew Chem Int Ed Engl. 2001 Jun 18;40(12):2311-2313. doi: 10.1002/1521-3773(20010618)40:12<2311::AID-ANIE2311>3.0.CO;2-T.

Authors

Michael G B Drew¹, Laurence M Harwood¹, Antonio J Macías-Sánchez¹, Richard Scott¹, R M Thomas², Daniel Uguen³

Affiliations

¹ Department of Chemistry, University of Reading Whiteknights, Reading RG6 6AD (UK) Fax: (+44) 1189-316-782.
² Astra-Zeneca Silk Road Business Park Macclesfield SK102NA (UK).
³ École de Chimie, des Polymères et des Matérieaux Laboratoire de Synthèse Organique 25 rue Becquerel, 67087 Strasbourg (France).

PMID: 29711837
DOI: 10.1002/1521-3773(20010618)40:12<2311::AID-ANIE2311>3.0.CO;2-T

Abstract

The diastereocomplementarity of halo- and alkylcarbenes (paths a and b, respectively) was shown in the cyclopropanation reaction of 1. The conversion of 1 into 7,7-dimethylbicyclo[4.1.0]heptan-1,2-diols (±)-2 and (±)-3 represents an important transformation in a synthetic strategy towards phorbol derivatives. TBDMS=tert-butyldimethylsilyl.

Keywords: carbenoids; cyclopropanations; diastereoselectivity; enol ethers; synthetic methods.