Metal Hydride (MH) Hydrogen Atom Transfer (HAT) (or MHAT). Classical hydrofunctionalization of alkenes requires strong Bronsted acids to form fleeting, high-energy carbocations. In contrast, non-canonical reactions of metal hydrides can hydrofunctionalize alkenes through lower-energy carbon-centered radicals.

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金属氢转移（MHAT）是金属（包括Fe, Mn, Co等）氢化物参与的氢原子转移（HAT, Hydrogen atom transfer）过程，通常用于烯烃的 马氏选择性 氢官能团化中。 [1] 该类反应一般有选择性强、条件温和、底物范围广和适合后期官能团化等特点，所以近些年MHAT反应发展迅速，得到了大量关注。 在有机方法学领域，代表金属氢转移的“MHAT”这个术语最早由Ryan A. Shenvi提出并使用。 但对过渡金属氢化物通过氢原子转移活化烯烃的机理研究可追溯至20世纪70年代，当时芝 …

最近， 美国莱斯大学的 Julian G. West课题组 实现了 协同氢原子转移（cHAT）进行烯烃还原的双重催化策略。 通过使用氢化物和质子作为氢原子源，两种HAT催化剂协同催化实现烯烃的还原。 相关研究成果发表在 J. Am. Chem. Soc. （DOI: 10.1021/jacs.0c09544）。 （图片来源: J. Am. Chem. Soc.） 首先， 作者对反应进行设计， 通过设计催化机理来消除化学计量的过氧化物。 作者在反应中引入催化剂 B-H，在第二个HAT步骤原位生成当量氧化剂，可以消除外加氧化剂。 …

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2023年6月16日 · Metal hydride hydrogen atom transfer (MH HAT) (86,87) chemistry has emerged as one of the most efficient tools for the donor HAT process in several alkene hydrofunctionalization reactions.