Origin of Stereocontrol in the Construction of the 12-oxatricyclo[6.3.1.0(2,7)]dodecane Ring System by Prins-pinacol Reactions

Overview

Journal J Org Chem

Publisher American Chemical Society

Specialty Chemistry

Date 2009 Dec 17

PMID 20000652

Citations 3

Authors

Larry E Overman

Paul S Tanis

Affiliations

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Abstract

Polycyclic products containing the 12-oxatricyclo[6.3.1.0(2,7)]dodecane moiety having either the trans (8a-e) or cis (9a-e) relative configuration of the oxacyclic bridge and the cis angular substituents are formed stereospecifically by Prins-pinacol cyclizations of unsaturated alpha-dithianyl acetals 14a-e or 15a-e. These results show that the topography (boat or chair) of the Prins cyclization of the sulfur-stabilized oxocarbenium ions generated from acetals 14a-e or 15a-e is controlled by the stereoelectronic influence of the allylic substituents, with steric effects playing a minor role. A complex molecular rearrangement that is terminated by a thio-Prins-pinacol reaction is also identified.

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