Reaction Pathways and Redox States in α-selective Cobalt-Catalyzed Hydroborations of Alkynes.,Angewandte Chemie International Edition

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Reaction Pathways and Redox States in α-selective Cobalt-Catalyzed Hydroborations of Alkynes.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-09-05 , DOI: 10.1002/anie.202009625
Clemens K Blasius ₁ , Vladislav Vasilenko ₁ , Regina Matveeva ₁ , Hubert Wadepohl ₁ , Lutz H Gade ₁

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Cobalt(II) alkyl complexes supported by a monoanionic NNN pincer ligand are pre‐catalysts for the regioselective hydroboration of terminal alkynes, yielding the Markovnikov products with α:β‐(E) ratios of up to 97:3. A cobalt(II) hydride and a cobalt(II) vinyl complex appear to determine the main reaction pathway. In a background reaction the highly reactive hydrido species specifically converts to a coordinatively unsaturated cobalt(I) complex which was found to re‐enter the main catalytic cycle.

中文翻译：

α选择性钴催化炔烃硼氢化反应中的反应途径和氧化还原态。

由单阴离子NNN钳形配体支撑的钴（II）烷基络合物是末端炔烃区域选择性氢硼化的预催化剂，产生的马尔可夫尼科夫产物的α：β-（E）比率高达97：3。氢化钴（II）和乙烯基钴（II）配合物似乎决定了主要的反应途径。在背景反应中，高反应性氢化物特异性地转化为配位不饱和钴（I）配合物，该配合物重新进入主催化循环。

更新日期：2020-09-05

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