Saha Sayantani, Eisen Moris S
Schulich Faculty of Chemistry, Technion - Israel Institute of Technology, Haifa City, 32000, Israel.
Dalton Trans. 2020 Sep 22;49(36):12835-12841. doi: 10.1039/d0dt02770g.
The organoactinide-catalyzed (Cp2ThMe2) hydroborated reduction of a wide range of tertiary, secondary, and primary amides to the corresponding amines/amine-borane adducts via deoxygenation of the amides is reported herein. The catalytic reactions proceed under mild conditions with low catalyst loading and pinacolborane (HBpin) concentration in a selective fashion. Cp2ThMe2 is capable of efficiently catalysing the gram-scale reaction without a drop in efficiency. The amine-borane adducts are successfully converted into free amine products in high conversions, which increases the usefulness of this catalytic system. A plausible mechanism is proposed based on detailed kinetics, stoichiometric, and deuterium labeling studies.
本文报道了有机锕系元素催化（Cp2ThMe2）的一系列叔酰胺、仲酰胺和伯酰胺通过酰胺脱氧反应，以选择性方式还原为相应的胺/胺-硼烷加合物。催化反应在温和条件下进行，催化剂负载量低，频哪醇硼烷（HBpin）浓度低。Cp2ThMe2能够有效催化克级反应，且效率不降低。胺-硼烷加合物能成功地高转化率转化为游离胺产物，这增加了该催化体系的实用性。基于详细的动力学、化学计量学和氘标记研究，提出了一个合理的机理。
