State Key Laboratory of Organometallic Chemistry , Shanghai Institute of Organic Chemistry , Chinese Academy of Sciences, 345 Lingling Lu , Shanghai 200032 , China.
Collaborative Innovation Center of Chemical Science and Engineering , Tianjin , 300072 , China.
Org Lett. 2019 Aug 2;21(15):6130-6134. doi: 10.1021/acs.orglett.9b02285. Epub 2019 Jul 18.
A highly enantioselective rhodium-catalyzed allylic dearomatization of β-naphthols with racemic aryl vinyl carbinol is described. In the presence of a Rh-catalyst derived from [Rh(CH)Cl] and chiral (P, olefin)-ligand with TFA as an additive, the functionalized β-naphthalenone compounds bearing an all-carbon-substituted quaternary stereogenic center were obtained in good yields with excellent enantioselectivity. In addition, this protocol features the enantioselective control of prochiral nucleophiles and provides the first illustration of Rh-catalyzed asymmetric allylic dearomatization.
描述了一种对映选择性的铑催化β-萘酚与外消旋芳基乙烯基甲醇的烯丙基去芳构化反应。在 Rh 催化剂[Rh(CH)Cl]和手性（P，烯烃）配体与 TFA 作为添加剂的存在下，功能化的β-萘满酮化合物在良好的收率下具有优异的对映选择性，带有全碳取代的季碳手性中心。此外，该方案具有对前手性亲核试剂的对映选择性控制，并提供了 Rh 催化不对称烯丙基去芳构化的首例实例。
