Cui Jin, Oriez Raphaël, Samanta Sadhanendu, Noda Hidetoshi, Watanabe Takumi, Shibasaki Masakatsu
Institute of Microbial Chemistry (BIKAKEN), Tokyo, 3-14-23 Kamiosaki Shinagawa-ku, Tokyo 141-0021, Japan.
Center for Innovative Drug Discovery, Greater Bay Area Institute of Precision Medicine (Guangzhou), School of Pharmacy, Fudan University, Shanghai 200437, P.R. China.
Org Lett. 2023 Nov 24;25(46):8367-8371. doi: 10.1021/acs.orglett.3c03503. Epub 2023 Nov 14.
A copper-catalyzed asymmetric vinylogous conjugate addition of butenolide to 2-ester-substituted chromones is described, and it delivers - or -chromanone lactones with high stereoselectivities. The enantioselectivity-determining step varied with the use of B(OMe) as an additive, resulting in enhanced stereoselectivities, as revealed by density functional theory calculations, which also provided theoretical insight into the origin of the ligand-dependent diastereodivergence.
本文描述了一种铜催化的丁烯内酯对2-酯基取代色酮的不对称烯丙基共轭加成反应，该反应能以高立体选择性生成α-或γ-色满酮内酯。使用B(OMe)₃作为添加剂时，对映选择性决定步骤会发生变化，从而提高了立体选择性，密度泛函理论计算揭示了这一点，该计算还为配体依赖性非对映选择性差异的起源提供了理论见解。
