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A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids to Form New Trisubstituted Olefins by Cross Metathesis
preprintrevised on 16.12.2019, 11:42 and posted on 23.12.2019, 06:15 by Karim Bahou, D. Christopher Braddock, Adam G. Meyer, G. Paul Savage, Zhensheng Shi, Tianyou He
Abstract: 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).