A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross-Metathesis with Trisubstituted Alkenes

A retrosynthetic disconnection–reconnection analysis of epoxypolyenessubstrates that can undergo cyclization to podocarpane-type tricyclesreveals relay-actuated Δ6,7-functionalized monoterpenoid alcohols for ruthenium benzylidene catalyzed olefin cross-metathesis with homoprenyl benzenes. Successf...

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Bibliographic Details
Published in:Journal of organic chemistry 2020-04, Vol.85 (7), p.4906-4917
Main Authors: Bahou, Karim A, Braddock, D. Christopher, Meyer, Adam G, Savage, G. Paul, Shi, Zhensheng, He, Tianyou
Format: Article
Language:English
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Summary:A retrosynthetic disconnection–reconnection analysis of epoxypolyenessubstrates that can undergo cyclization to podocarpane-type tricyclesreveals relay-actuated Δ6,7-functionalized monoterpenoid alcohols for ruthenium benzylidene catalyzed olefin cross-metathesis with homoprenyl benzenes. Successful implementation of this approach provided several epoxypolyenes as expected (E/Z, ca. 2–3:1). The method is further generalized for the cross-metathesis of pre-existing trisubstituted olefins in other relay-actuated Δ6,7-functionalized monoterpenoid alcohols with various other trisubstituted alkenes to form new trisubstituted olefins. Epoxypolyene cyclization of an enantiomerically pure, but geometrically impure, epoxypolyene substrate provides an enantiomerically pure, trans-fused, podocarpane-type tricycle (from the E-geometrical isomer).
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.0c00067