Palladium-Catalysed Intramolecular Cyclisations of Olefinic Propargylic Carbonates and Application to the Diastereoselective Synthesis of Enantiomerically pure (-)-α-Thujone

Von Oppolzer, Wolfgang; Pimm, Austen David; Stammen, Blanda Luzia Christa; Hume, Ewan

doi:10.1002/hlca.19970800302

Scientific article

English

Palladium-Catalysed Intramolecular Cyclisations of Olefinic Propargylic Carbonates and Application to the Diastereoselective Synthesis of Enantiomerically pure (-)-α-Thujone

ContributorsVon Oppolzer, Wolfgang; Pimm, Austen David; Stammen, Blanda Luzia Christa; Hume, Ewan

Published inHelvetica Chimica Acta, vol. 80, no. 3, p. 623-639

Publication date1997

Abstract

Intramolecular [Pd2(dba)3]/tri(2‐furyl)phosphine‐catalysed (dba = dibenzylideneacetone, PhCH=CHCOCH=CHPh) cyclisations of olefinic propargylic carbonates I provided alk‐1‐enyl‐(3‐aza)bicyclo[3.1.0]‐hexanes VIII in good yields. A palladium cascade sequence I → II → III → IV → VII → VIII is proposed. Furthermore, chiral propargylic carbonates such as 23, 24 and 25 allowed diastereoselective formation of bicyclo[3.1.0]hexanes 29, 30 and 31, respectively. The first diastereoselective synthesis of the monoterpene, (−)‐α‐thujone 40 illustrates the potential of the method.

Affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

Citation (ISO format)

VON OPPOLZER, Wolfgang et al. Palladium-Catalysed Intramolecular Cyclisations of Olefinic Propargylic Carbonates and Application to the Diastereoselective Synthesis of Enantiomerically pure (-)-α-Thujone. In: Helvetica Chimica Acta, 1997, vol. 80, n° 3, p. 623–639. doi: 10.1002/hlca.19970800302

Article (Published version)

Identifiers

PID : unige:131605
DOI : 10.1002/hlca.19970800302

Additional URL for this publicationhttp://doi.wiley.com/10.1002/hlca.19970800302

Journal ISSN0018-019X

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Palladium-Catalysed Intramolecular Cyclisations of Olefinic Propargylic Carbonates and Application to the Diastereoselective Synthesis of Enantiomerically pure (-)-α-Thujone

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