LiAlH4: From Stoichiometric Reduction to Imine Hydrogenation Catalysis
LiAlH4: From Stoichiometric Reduction to Imine Hydrogenation Catalysis
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DOI：
10.1002/anie.201803804
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发表时间：
2018-06-11
影响因子：
16.6
通讯作者：
Harder, Sjoerd
中科院分区：
文献类型：
--
作者：
Elsen, Holger;Faerber, Christian;Harder, Sjoerd
用催化代替化学计量量的LiAlH4进行亚胺到胺的转化（85℃，催化剂负载2.5mol%，压力1bar）。讨论了温度、压力、溶剂和催化剂改性以及衬底范围的影响。实验研究和初步DFT计算表明，催化活性物质是在原位生成的：LiAlH4+Ph(H)C=NtBuLiAlH(2)[N(tBu)CH2Ph](2)。提出了一种Li和Al都发挥突出作用的合作机制。
Imine-to-amine conversion with catalytic instead of stoichiometric quantities of LiAlH4 is demonstrated (85 degrees C, catalyst loading2.5mol%, pressure1bar). 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 insitu: LiAlH4+Ph(H)C=NtBuLiAlH(2)[N(tBu)CH2Ph](2). A cooperative mechanism in which Li and Al both play a prominent role is proposed.