钴催化可见光驱动还原氢甲酰化合成醇。
Alcohol Synthesis by Cobalt-Catalyzed Visible-Light-Driven Reductive Hydroformylation.
机构信息
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
出版信息
J Am Chem Soc. 2022 Oct 26;144(42):19219-19224. doi: 10.1021/jacs.2c07745. Epub 2022 Oct 14.
A cobalt-catalyzed reductive hydroformylation of terminal and 1,1-disubstituted alkenes is described. One-carbon homologated alcohols were synthesized directly from CO and H, affording anti-Markovnikov products (34-87% yield) with exclusive regiocontrol (linear/branch >99:1) for minimally functionalized alkenes. Irradiation of the air-stable cobalt hydride, (dcype)Co(CO)H (dcype = dicyclohexylphosphinoethane) with blue light generated the active catalyst that mediates alkene hydroformylation and subsequent aldehyde hydrogenation. Mechanistic origins of absolute regiocontrol were investigated by monitoring of the tandem catalytic reaction using multinuclear NMR spectroscopy with syngas mixtures.
描述了钴催化的末端和 1,1-取代烯烃的还原氢甲酰化反应。一碳同系化醇可直接由 CO 和 H 合成，对最小官能化烯烃具有独特的区域选择性（线性/支化 >99:1），得到反马氏加成产物（产率 34-87%）。用蓝光照射空气稳定的钴氢化物(dcype)Co(CO)H（dcype = 二环己基膦乙烷），生成了活性催化剂，可介导烯烃氢甲酰化和随后的醛加氢。通过使用含有 syngas 混合物的多核 NMR 光谱监测串联催化反应，研究了绝对区域选择性的机械起源。
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