2020
DOI: 10.1021/acs.joc.0c00067
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A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross-Metathesis with Trisubstituted Alkenes

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-actuat… Show more

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Cited by 9 publications
(8 citation statements)
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“…However, despite the long-term recognition that these linear compounds are essentially C 5 -repeating isoprene units, a general and iterative chemical protocol for their synthesis using naturally occurring, terpenoid building blocks does not exist . We recently reported an olefin cross metathesis reaction between relay-actuated Δ 6,7 -functionalized monoterpenoid alcohols with trisubstituted alkenes as partner olefins to form new trisubstituted alkenes (Figure b) . We now report that the use of readily available and nonexpensive citral as the partner olefina monoterpenoid with two electronically distinguishable alkenesallows for the iterative construction of terpenoids in line with the above aims (Figure c) .…”
supporting
confidence: 76%
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“…However, despite the long-term recognition that these linear compounds are essentially C 5 -repeating isoprene units, a general and iterative chemical protocol for their synthesis using naturally occurring, terpenoid building blocks does not exist . We recently reported an olefin cross metathesis reaction between relay-actuated Δ 6,7 -functionalized monoterpenoid alcohols with trisubstituted alkenes as partner olefins to form new trisubstituted alkenes (Figure b) . We now report that the use of readily available and nonexpensive citral as the partner olefina monoterpenoid with two electronically distinguishable alkenesallows for the iterative construction of terpenoids in line with the above aims (Figure c) .…”
supporting
confidence: 76%
“…To commence our investigations enantiopure epoxide 2 , as a relay-actuated Δ 6,7 -functionalized monoterpenoid derivative, was prepared from diol 1 using the method of Corey et al (Scheme ). Using our previously identified conditions (10 mol % ruthenium benzylidene precatalyst 5 , alkene [5 equiv], 50 °C, 1 h), attempted relay cross metathesis reaction between epoxide 2 and citral ( 3 ) , to give C 15 -sesquiterpenoid 4 using 5 was unsuccessful (Table , entry 1). Further attempts with 10 equiv of 3 (entry 2) or at room temperature (entry 3) or with 2 mol % catalyst loading (entry 4) also failed.…”
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confidence: 99%
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