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제116회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Synergistic Rh/Pd Dual Catalysis: Chemo- and Stereoselective Coupling between Rh(II)-Carbenes and ?-Allyl Pd(II) Complexes

2015년 9월 3일 15시 26분 02초
ORGN.P-427 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
10월 15일 (목요일) 11:00~12:30
저자 및
Chen zisheng, 이상기1,*
이화여자대학교, China
1이화여자대학교 화학/나노과학과, Korea

Synergistic dual catalysis has emerged as a new and powerful strategy in chemical synthesis.1 In this dual catalytic process, each catalyst could selectively activate the substrates to enable the chemical transformations that are not possible with either one of the catalysts.1 The main challenge for the development of synergistic catalysis is ensuring catalyst cross-compatibility, balancing kinetics for substrate activation and avoiding catalyst deactivation. Here we present a novel synergistic Rh(II)/Pd(0) dual catalysis strategy that promotes the denitrogenative cross-coupling of 1-sulfonyl-1,2,3-triazoles 1 with allyl carboxylates, which does not occur when using a Rh(II) or Pd(0) catalyst alone. In this dual catalysis process, Rh(II) and Pd(0) catalysts activate 1-sulfonyl-1,2,3-triazoles and allyl carboxylates in a substrate-selective manner with balanced-kinetics to generate an ?-imino Rh(II)-carbene and a ?-allyl Pd(II)-complex. Coordination of the pendant ?-imine of the Rh(II)-carbene with the Lewis acidic Pd-complex plays a key role in not only placing the activated species in proximity but also in reversing electronic nature of the Pd-complex, which may facilitate the nucleophilic transfer of the carboxylate onto the electrophilic carbenic carbon. This effectively accomplishes the formal 1,3-insertion of ?-imino Rh(II)-carbenes into the sp3 C?O bond of allyl carboxylates to yield N-allylated (Z)-amino vinyl carboxylates (Scheme 1).2 (1) Allen, A. EMacMillan, .; D. W. C. Chem. Sci. 2012, 3, 633-658. (2) Chen, Z.-S.; Jeon, H. J.; Chen, S.-W.; Xuan, Z.; Lee, S.-g. 2015, manuscript submitted.