Samanta Sadhanendu, Cui Jin, Noda Hidetoshi, Watanabe Takumi, Shibasaki Masakatsu
Institute of Microbial Chemistry, Tokyo 141-0021, BIKAKEN, Japan.
J Org Chem. 2023 Jan 20;88(2):1177-1184. doi: 10.1021/acs.joc.2c02731. Epub 2023 Jan 9.
A gram-scale -selective asymmetric vinylogous addition of butenolides to chromones, catalyzed by an Al-Li-BINOL (ALB) complex, was developed in this study. For various combinations of substrates, the observed diastereoselectivity approached 20:1 with 84-98% ee. This protocol is complementary to previously reported ones and improves the selectivity for several chromones. This methodology can be applied to a quinolone substrate, affording another type of heterocyclic scaffolds substituted with five-membered lactones. Computational studies support the role of ALB as a bifunctional catalyst in this reaction and provide insights into the origin of the observed stereoselectivity.
本研究开发了一种由铝-锂-联萘酚（ALB）络合物催化的克级规模的丁烯内酯对色酮的选择性不对称乙烯型加成反应。对于各种底物组合，观察到的非对映选择性接近20:1，对映体过量率为84-98%。该方法与先前报道的方法互补，并提高了几种色酮的选择性。该方法可应用于喹诺酮底物，得到另一种被五元内酯取代的杂环骨架。计算研究支持了ALB在该反应中作为双功能催化剂的作用，并为观察到的立体选择性起源提供了见解。
