[논문]The site-selectivity and mechanism of Pd-catalyzed C(sp 2 )–H arylation of simple arenes

Kim, Daeun; Choi, Geunho; Kim, Weonjeong; Kim, Dongwook; Kang, Youn K.; Hong, Soon Hyeok

doi:10.1039/d0sc05414c

[해외논문] The site-selectivity and mechanism of Pd-catalyzed C(sp 2 )–H arylation of simple arenes 원문보기

Chemical science, v.12 no.1, 2021년, pp.363 - 373

Kim, Daeun (Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of Korea soonhyeok.hong@kaist.ac.kr) , Choi, Geunho (Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of Korea soonhyeok.hong@kaist.ac.kr) , Kim, Weonjeong (Department of Chemistry, College of Natural Sciences, Seoul National University Seoul 08826 Republic of Korea) , Kim, Dongwook (Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS) Daejeon 34141 Republic of Korea) , Kang, Youn K. (Department of Chemical Energy Engineering, Sangmyung University Seoul 03016 Korea) , Hong, Soon Hyeok (Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of Korea soonhyeok.hong@kaist.ac.kr Republic of Ko)

Abstract ▼ AI-Helper

Control over site-selectivity is a critical challenge for practical application of catalytic C–H functionalization reactions in organic synthesis. Despite the seminal breakthrough of the Pd-catalyzed C(sp2)–H arylation of simple arenes via a concerted metalation–deprotonation (CMD) pathway in 2006, understanding the site-selectivity of the reaction still remains elusive. Here, we have comprehensively investigated the scope, site-selectivity, and mechanism of the Pd-catalyzed direct C–H arylation reaction of simple arenes. Counterintuitively, electron-rich arenes preferably undergo meta-arylation without the need for a specifically designed directing group, whereas electron-deficient arenes bearing fluoro or cyano groups exhibit high ortho-selectivity and electron-deficient arenes bearing bulky electron-withdrawing groups favor the meta-product. Comprehensive mechanistic investigations through a combination of kinetic measurements and stoichiometric experiments using arylpalladium complexes have revealed that the Pd-based catalytic system works via a cooperative bimetallic mechanism, not the originally proposed monometallic CMD mechanism, regardless of the presence of a strongly coordinating L-type ligand. Notably, the transmetalation step, which is influenced by a potassium cation, is suggested as the selectivity-determining step.The transmetalation step, not the C–H activation step, is suggested as the selectivity-determining step in Pd-catalyzed C–H arylation of simple arenes.

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