The implementation of earth-abundant metals mediated chemistry is a major goal in homogeneous catalysis. Borrowing hydrogen/hydrogen autotransfer (BH/HA) reaction, as a straightforward and sustainable synthetic method, has attracted considerable attention in the development of earth-abuandant metal catalysts. Herein, we report a tungsten-catalyzed N-alkylation reaction of amines with primary alcohols via BH/HA. This phosphine-free W(phen)(CO)₄ (phen=1,10-phenthroline) system was demonstrated as a practical and easily accessible in-situ catalysis for a broad range of amines and alcohols (up to 49 examples, including 16 previously undisclosed products). Notably, this tungsten system can tolerate numerous functional groups, especially the challenging substrates with sterically hindered substituents, or heteroatoms. Mechanistic insights based on experimental and computational studies are also provided.

中文翻译：

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钨催化的醇与胺直接N-烷基化

稀土金属介导化学的实现是均相催化的主要目标。借用氢/氢自转移（BH / HA）反应作为一种简单，可持续的合成方法，在富土金属催化剂的开发中引起了相当大的关注。本文中，我们报道了通过BH / HA的钨与伯醇的钨催化N烷基化反应。该无膦的W（phen）（CO）₄ （phen = 1,10-phenthroline）系统被证明是一种实用且易于就地获得的系统催化作用的胺和醇种类繁多（多达49个实例，包括16个以前未公开的产品）。值得注意的是，该钨系统可以耐受许多官能团，尤其是具有位阻取代基或杂原子的具有挑战性的底物。还提供了基于实验和计算研究的力学见解。