金（I）催化的炔丙基苯甲酰胺环化反应速率决定步骤中溶剂依赖性变化
Solvent-Dependent Change in the Rate-Determining Step of Au(I)-Catalyzed -Propargyl Benzamide Cyclization.
作者信息
Norman Skylar G, Jiao Lin, Yi Jun, Liu Leo, Ding Wendu, Jones Amanda C
机构信息
Department of Chemistry, Wake Forest University, 1834 Wake Forest Road, Winston-Salem, North Carolina 27109, United States.
Department of Chemistry and the Center for Functional Materials, Wake Forest University, Winston-Salem, North Carolina 27109, United States.
出版信息
J Org Chem. 2025 Aug 8;90(31):11068-11073. doi: 10.1021/acs.joc.5c00787. Epub 2025 Jul 28.
The cyclization of -propargyl benzamide with gold catalysts has become a popular benchmark reaction over the past two decades. The prevailing consensus denotes protodeauration as rate-limiting. Cyclization with [Au(NCCH)]SbF and AuOTs ( = -Bu(-biphenyl)P, also known as Johnphos) in dichloromethane and methanol in conjunction with deuterium labeling studies reveals a solvent-dependent switch to π-activation for the rate-limiting step. Computational calculations support this change of the rate-determining step.
在过去二十年中，使用金催化剂使炔丙基苯甲酰胺环化已成为一个广受欢迎的基准反应。目前普遍的共识是，质子脱金反应是限速步骤。在二氯甲烷和甲醇中使用[Au(NCCH₃)]SbF₆和AuOTs（L = t-Bu(o-biphenyl)P，也称为Johnphos）进行环化反应，并结合氘标记研究表明，限速步骤存在溶剂依赖性的向π-活化的转变。计算计算支持了速率决定步骤的这种变化。
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