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A relay strategy actuates pre-existing trisubstituted olefins in monoterpenoids for cross metathesis with trisubstituted alkenes

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Title: A relay strategy actuates pre-existing trisubstituted olefins in monoterpenoids for cross metathesis with trisubstituted alkenes
Authors: Bahou, K
Braddock, D
Meyer, A
Savage, P
Shi, Z
He, T
Item Type: Journal Article
Abstract: A retrosynthetic disconnection-reconnection analysis of epoxypolyenes – substrates that can undergo cyclization to podocarpane-type tricycles – reveals relay-actuated 6,7-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 6,7-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).
Issue Date: 19-Mar-2020
Date of Acceptance: 5-Mar-2020
URI: http://hdl.handle.net/10044/1/77166
DOI: 10.1021/acs.joc.0c00067
ISSN: 0022-3263
Publisher: American Chemical Society
Start Page: 4906
End Page: 4917
Journal / Book Title: The Journal of Organic Chemistry
Volume: 85
Issue: 7
Copyright Statement: © 2020 American Chemical Society. This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html), which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
Sponsor/Funder: Engineering & Physical Science Research Council (EPSRC)
Funder's Grant Number: EP/P030742/1
Keywords: Science & Technology
Physical Sciences
Chemistry, Organic
Chemistry
RING-CLOSING METATHESIS
FORMAL SYNTHESIS
ASYMMETRIC DIHYDROXYLATION
ALLYLIC HALIDES
ALKYLATION
EFFICIENT
ALCOHOLS
DITERPENOIDS
CYCLIZATIONS
SELECTIVITY
0304 Medicinal and Biomolecular Chemistry
0305 Organic Chemistry
Organic Chemistry
Publication Status: Published
Online Publication Date: 2020-03-19
Appears in Collections:Chemistry
Faculty of Natural Sciences