Building up molecular complexity by Ni-catalyzed cross-coupling reactions

Identifier:  TDX:3374

Handle: https://hdl.handle.net/20.500.11797/TDX3374

Authors:  Sun, Shangzheng

Abstract:
In line with our group research interests on cross-coupling-reactions, we decided to focus this doctoral studies on the development of sp3 C–C bond formation by means of nickel catalyzed reductive-cross-coupling. Our first effort was focused on the development of a reductive alkylation of a-haloboronates with unactivated olefin feedstocks. We have developed a mild, chemo- and site-selective catalytic protocol that allows the incorporation of an alkylboron fragment into unactivated olefins. Moreover, the use of internal olefins enables C C bond-formation at remote sp3 C-H sites via nickel catalyzed chain-walking process. Following up our interest on nickel catalyzed chainwalking events, we reported a site-selective catalytic deaminative alkylation of unactivated olefins. This method operates under mild conditions and is characterized by a wide substrate scope and exquisite site-selectivity profile. Particularly noteworthy is that this technique could be employed in the context of ethylene derivatization and for the late-stage functionalization of complex molecules. Our final efforts for the sp3 C–C bond formation was focused on the development of a regio-selective cross-coupling of three electrophiles by means of nickel/photoredox dual catalysis. We developed a modular, chemo- and regio-selective 1,2-difunctionalization of simple vinyl boronates with readily available organic halides.