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Several cobalt complexes bearing tridentate (NNN) ligands were synthesized and served as precatalysts for alkyne hydrosilylation with Ph2SiH2. For terminal alkynes, the catalyst L2 b‐CoCl2 was selected, and resulted in the corresponding α‐vinylsilanes with high (Markovnikov) regioselectivity and extensive functional‐group tolerance. For internal diaryl alkynes, the catalyst L2 c‐CoCl2 exhibited the best activity, and afforded E‐selective vinylsilanes through syn‐addition in excellent yield under mild conditions. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(43):13586-13590
A variety of terminal and internal alkynes were converted regio‐ and stereoselectively into (Z )‐3‐chloroacrylonitriles by treatment with BCl3 in the presence of stoichiometric amounts of imidazolium thiocyanates. These products could be readily functionalized to provide useful building blocks, thus demonstrating the synthetic value of the method. Preliminary mechanistic studies suggest initial activation of the cationic thiocyanate by the Lewis acid, followed by electrophilic attack of the alkyne. The syn addition of a chloride to the vinyl cation intermediate and final elimination of the thiourea unit afford the desired chloroacrylonitriles. 相似文献
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Nobuyoshi Nomura Ko Tsurugi Masahiko Okada 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2001,113(10):1986-1989