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A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross-Metathesis with Trisubstituted Alkenes.
The Journal of Organic Chemistry ( IF 3.6 ) Pub Date : 2020-03-19 , DOI: 10.1021/acs.joc.0c00067
Karim A Bahou 1 , D Christopher Braddock 1 , Adam G Meyer 2 , G Paul Savage 2 , Zhensheng Shi 1 , Tianyou He 1
Affiliation  

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).

中文翻译:

中继策略可激活单萜类化合物中预先存在的三取代烯烃与三取代烯烃的交叉复分解。

环氧多烯-底物的逆合成断开-重新连接分析,该底物可以环化为罗汉木烷型三环-揭示了中继驱动的Δ6,7-官能化单萜类醇用于钌亚苄基催化的烯烃与异戊二烯苯的交叉复分解。该方法的成功实施提供了预期的几种环氧多烯(E / Z,约2-3:1)。该方法被进一步推广用于在其他中继活化的Δ6,7-官能化单萜类醇中与预先存在的三取代烯烃与各种其他三取代烯烃的交叉复分解反应,以形成新的三取代烯烃。对映体纯净但几何形状不纯的环氧多烯底物的环氧多烯环化提供了对映体纯的,反式稠合的,罗丹烷型三轮车(来自E几何异构体)。
更新日期:2020-03-20
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