Faculty of Pharmaceutical Sciences , Hokkaido University , Nishi 6, Kita 12 , Kita-ku , Sapporo 060-0812 , Japan.
Org Lett. 2019 Jun 7;21(11):4120-4123. doi: 10.1021/acs.orglett.9b01307. Epub 2019 May 29.
Rhodium(I)-catalyzed enantioselective hydroacylation of 4-allenals was found to proceed smoothly, giving six-membered ketones in good yields (up to 84% yield) with high enantiomeric excess (up to 96% ee) even from racemic allenes as substrates. Mechanistic studies revealed that racemization of the allene moiety in the substrate would occur via a dynamic kinetic resolution (DKR) process during the hydroacylation.
铑（I）催化的 4-烯丙基醛的对映选择性氢甲酰化反应进行得很顺利，即使使用外消旋的烯丙基作为底物，也能以高收率（高达 84%）和高对映选择性（高达 96%ee）得到六元酮。机理研究表明，在氢甲酰化过程中，底物中烯丙基部分的外消旋化会通过动态动力学拆分（DKR）过程发生。
