作者:Valeriy Cherepakhin、Travis J. Williams
DOI:10.1021/acscatal.9b03679
日期:2020.1.3
catalyst evolution for our ruthenium-based coupling of amines and alcohols, which proceeds from a [(η6-cymene)RuCl(PyCH2PtBu2)]OTf (1) precatalyst. The method selectively produces secondary amines through a hydrogen borrowing mechanism and is successfully applied to several heterocyclic carbinol substrates. Under the reaction conditions, precatalyst 1 evolves through a series of catalytic intermediates:
我们描述了机构,范围,和用于胺和醇的我们的基于钌的耦合,其中从[(η前进催化剂进化6 -cymene)的RuCl(PyCH 2 P吨卜2)]光学传递函数(1)预催化剂。该方法通过氢借位机理选择性地产生仲胺,并成功地应用于几种杂环甲醇底物。在反应条件下,预催化剂1周的演进通过一系列催化中间体:[(η 6 -cymene)期RuH(PyCH 2 P吨卜2)]光学传递函数(3),的[Ru 3 ħ 2氯2(CO)(PyCH 2 P t Bu 2)2 μ-(C 5 H 3 N)CH 2 P t Bu 2 }] OTf(4)和[Ru 2 HCl(CO)2(PyCH 2 P吨卜2)2(μ-O 2 C ^ ñ PR)] X(反式- 5,X =氯;顺式- 6,X = OTF)。4和6的结构通过单晶X射线衍射确定。对催化活性的研究表明,4是催化剂的休眠(但活着)形式,而5和6是最终的死形式。电化学研究表明,4在CH