Liang Xiao, Wei Kun, Yang Yu-Rong
State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650201, China.
Chem Commun (Camb). 2015 Dec 21;51(98):17471-4. doi: 10.1039/c5cc07221b. Epub 2015 Oct 19.
The unified Ir-catalyzed enantioselective allylic substitution reactions of silyl enol ethers derived from ketones and α,β-unsaturated ketones with branched, racemic allylic alcohols are described. This transformation is catalyzed by the Carreira system and proceeds without fluoride, and with high ee and b : l ratio. The synthetic utility of this method was illustrated by the concise enantioselective total synthesis of marine natural products calyxolane A, B and by the assignment of the absolute configuration of calyxolane A.
本文描述了由酮和α,β-不饱和酮衍生的硅烯醇醚与支链外消旋烯丙醇的统一铱催化对映选择性烯丙基取代反应。该转化由卡雷拉体系催化，无需氟化物参与，且对映体过量值（ee）高，非对映体比例（b∶l）高。通过对海洋天然产物杯萼烷A、B进行简洁的对映选择性全合成以及确定杯萼烷A的绝对构型，证明了该方法的合成实用性。
