A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross-Metathesis with Trisubstituted Alkenes
A retrosynthetic disconnection–reconnection analysis of epoxypolyenessubstrates that can undergo cyclization to podocarpane-type tricyclesreveals relay-actuated Δ6,7-functionalized monoterpenoid alcohols for ruthenium benzylidene catalyzed olefin cross-metathesis with homoprenyl benzenes. Successf...
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| Veröffentlicht in: | Journal of organic chemistry 2020-04, Vol.85 (7), p.4906-4917 |
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| container_title | Journal of organic chemistry |
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| creator | Bahou, Karim A Braddock, D. Christopher Meyer, Adam G Savage, G. Paul Shi, Zhensheng He, Tianyou |
| description | A retrosynthetic disconnection–reconnection analysis of epoxypolyenessubstrates that can undergo cyclization to podocarpane-type tricyclesreveals 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). |
| doi_str_mv | 10.1021/acs.joc.0c00067 |
| format | Article |
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Christopher ; Meyer, Adam G ; Savage, G. Paul ; Shi, Zhensheng ; He, Tianyou</creator><creatorcontrib>Bahou, Karim A ; Braddock, D. Christopher ; Meyer, Adam G ; Savage, G. Paul ; Shi, Zhensheng ; He, Tianyou</creatorcontrib><description>A retrosynthetic disconnection–reconnection analysis of epoxypolyenessubstrates that can undergo cyclization to podocarpane-type tricyclesreveals 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. 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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. 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Paul</creatorcontrib><creatorcontrib>Shi, Zhensheng</creatorcontrib><creatorcontrib>He, Tianyou</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>AGRICOLA</collection><collection>AGRICOLA - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Bahou, Karim A</au><au>Braddock, D. Christopher</au><au>Meyer, Adam G</au><au>Savage, G. Paul</au><au>Shi, Zhensheng</au><au>He, Tianyou</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross-Metathesis with Trisubstituted Alkenes</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2020-04-03</date><risdate>2020</risdate><volume>85</volume><issue>7</issue><spage>4906</spage><epage>4917</epage><pages>4906-4917</pages><issn>0022-3263</issn><issn>1520-6904</issn><eissn>1520-6904</eissn><abstract>A retrosynthetic disconnection–reconnection analysis of epoxypolyenessubstrates that can undergo cyclization to podocarpane-type tricyclesreveals 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).</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>32191466</pmid><doi>10.1021/acs.joc.0c00067</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0001-7805-8630</orcidid><orcidid>https://orcid.org/0000-0001-6320-4201</orcidid><orcidid>https://orcid.org/0000-0002-4161-7256</orcidid><orcidid>https://orcid.org/0000-0002-8302-5283</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | alcohols benzene catalytic activity chemical reactions isomers monoterpenoids olefin organic chemistry ruthenium |
| title | A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross-Metathesis with Trisubstituted Alkenes |
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