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Iridium(III)-Catalyzed Asymmetric Site-Selective Carbene C–H Insertion during Late-Stage Transformation

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journal contribution
posted on 2022-05-03, 21:09 authored by Yuki Yamakawa, Takashi Ikuta, Hiroki Hayashi, Keigo Hashimoto, Ryoma Fujii, Kyohei Kawashima, Seiji Mori, Tatsuya Uchida, Tsutomu Katsuki
C–H functionalization has recently received considerable attention because C–H functionalization during the late-stage transformation is a strong and useful tool for the modification of the bioactive compounds and the creation of new active molecules. Although a carbene transfer reaction can directly convert a C–H bond to the desired C–C bond in a stereoselective manner, its application in late-stage material transformation is limited. Here, we observed that the iridium–salen complex 6 exhibited efficient catalysis in asymmetric carbene C–H insertion reactions. Under optimized conditions, benzylic, allylic, and propargylic C–H bonds were converted to desired C–C bonds in an excellent stereoselective manner. Excellent regioselectivity was demonstrated in the reaction using not only simple substrate but also natural products, bearing multiple reaction sites. Moreover, based on the mechanistic studies, the iridium-catalyzed unique C–H insertion reaction involved rate-determining asynchronous concerted processes.