Elsen Holger, Färber Christian, Ballmann Gerd, Harder Sjoerd
Inorganic and Organometallic Chemistry, Universität Erlangen-Nürnberg, Egerlandstrasse 1, 91058, Erlangen, Germany.
Angew Chem Int Ed Engl. 2018 Jun 11;57(24):7156-7160. doi: 10.1002/anie.201803804. Epub 2018 May 15.
Imine-to-amine conversion with catalytic instead of stoichiometric quantities of LiAlH is demonstrated (85 °C, catalyst loading≥2.5 mol %, pressure≥1 bar). The effects of temperature, pressure, solvent, and catalyst modifications, as well as the substrate scope are discussed. Experimental investigations and preliminary DFT calculations suggest that the catalytically active species is generated in situ: LiAlH +Ph(H)C=NtBu→LiAlH [N(tBu)CH Ph] . A cooperative mechanism in which Li and Al both play a prominent role is proposed.
已证明使用催化量而非化学计量的LiAlH可实现亚胺到胺的转化（85°C，催化剂负载量≥2.5 mol%，压力≥1 bar）。讨论了温度、压力、溶剂、催化剂改性的影响以及底物范围。实验研究和初步的密度泛函理论计算表明，催化活性物种是原位生成的：LiAlH + Ph(H)C=NtBu→LiAlH [N(tBu)CH Ph]。提出了一种Li和Al都起重要作用的协同机制。
