期刊
ACS CATALYSIS
卷 13, 期 10, 页码 6994-7001出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.3c00539
关键词
nickel catalysis; alkyne hydrophosphination; anti-Markovnikov; DFT calculation; P-stereogenic phosphines; alkenyl phosphine
A mechanism-inspired, reaction mode-controlled enantio- and regioselective anti-Markovnikov hydrophosphination of unactivated alkynes was achieved using NiII catalysis. Alkenyl phosphine products with high selectivity were obtained and easily diversified into structurally diverse chiral phosphine compounds.
A mechanism-inspired, reaction mode-controlled enantio-and regioselective anti-Markovnikov hydrophosphination of unactivated alkynes was accomplished by NiII catalysis. Alkenyl phosphine products could be obtained with high regio-and enantioselectivity and easily derivatized to structurally diverse chiral phosphine compounds. Mechanistic studies on both Ni0- catalyzed Markovnikov addition and NiII-catalyzed anti-Markovni-kov addition have been carried out by combining experimental and computational methods. In the Ni0 system, an allyl nickel complex was obtained as the catalyst resting state whose structure was unambiguously determined by single-crystal XRD analysis. A sequential hydrometallation, ligand exchange, and reductive elimination mechanism was elucidated corroboratively by DFT calculations. In the NiII system, the cationic secondary phosphine nickel complex serves as the active catalyst. A migratory insertion and protonation sequence was operative to accomplish anti-Markovnikov hydrophosphination.
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