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Diastereodivergent Hydrosilylative Enyne Cyclization Catalyzed by N ‐Heterocyclic Carbene‐Ni (0) †
Author(s) -
Yu Meng,
Yong Xuefeng,
Gao Weiwei,
Ho ChunYu
Publication year - 2021
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.202000651
Subject(s) - chemistry , enyne , carbene , alkyne , catalysis , silane , hydrosilylation , alkene , vinylsilane , ligand (biochemistry) , medicinal chemistry , stereocenter , reactivity (psychology) , stereochemistry , organic chemistry , enantioselective synthesis , receptor , medicine , biochemistry , alternative medicine , pathology
Main observation and conclusion Catalytic diastereodivergent hydrosilylative enyne cyclization with high generality and broad scope was achieved using electronic activated N ‐heterocyclic carbene‐Ni(0) as a catalyst and R 3 SiH as silane (IPr Cl , syn ‐ : anti ‐selectivity from up to 98 : 2 to 7 : 93 by Z = O, NH vs . NMs, R 1 = n ‐pentyl). Heterocycles bearing homoallylsilane rather than vinylsilane was obtained chemoselectively. The undesired yet highly competitive reactivity was suppressed, like direct hydrosilylation of alkene and alkyne concurrently. Optionally, the homoallylsilane products could be reduced further in one‐pot using IPr Me as ligand and (EtO) 3 SiH as silane under otherwise the same standard condition as the above, offering practical access to additional stereocenters and more diverse product structures from enynes.