Catalytic Asymmetric Halogenation/Semipinacol Rearrangement of 3‐Hydroxyl‐3‐vinyl Oxindoles: A Stereodivergent Kinetic Resolution Process
Li Dai, Wen Liu, Yuqiao Zhou, Zi Zeng, Xinyue Hu, Weidi Cao, Xiaoming Feng
Abstract
Abstract A highly enantioselective halogenation/semipinacol rearrangement of isatin‐derived allylic alcohols has been developed with a chiral N , N ′‐dioxide/Sc III complex as catalyst. This strategy involved a pivotal stereodivergent kinetic resolution process and provided a facile and efficient entry to optically active halo‐substituted quinolone derivatives and quinoline alkaloids with a quaternary stereocenter simultaneously under mild reaction conditions. Based on the control experiments together with kinetic studies and DFT calculations, a possible catalytic cycle was proposed to illustrate the reaction process and enantiocontrol.
Topics & Concepts
Kinetic resolutionStereocenterHalogenationEnantioselective synthesisChemistryAllylic rearrangementCombinatorial chemistryCatalysisCatalytic cycleOrganic chemistryAsymmetric Synthesis and CatalysisOxidative Organic Chemistry ReactionsAlkaloids: synthesis and pharmacology