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The mechanism of carboxylative cyclization of propargylamine by N-heterocyclic carbene complexes of Au(I).
Journal of Organometallic Chemistry ( IF 2.1 ) Pub Date : 2020-10-19 , DOI: 10.1016/j.jorganchem.2020.121583
Jack V. Davis , Mohan M. Gamage , Oswaldo Guio , Tahani A.C.A. Bayrakdar , Steven P. Nolan , Manuel Temprado , Burjor Captain , Carl D. Hoff

The complex [Au(IPr)(2-oxazolidinone)] (1 = IKa) was prepared from reaction of [Au(IPr)Cl] (2), K2CO3, and propargyl amine (PPA). Kinetic studies have been performed for acid cleavage of 1 to yield the oxazolidinone product and an [Au(IPr)(X)] adduct. The fastest rates of cleavage were found to occur for the hydrogen chloride salt of PPA (PPA-HCl) and for the CO2 adduct of PPA, PPA-CO2 = the carbamic acid (CA). This transformation was studied as a function of [CA], pressure of CO2 as well as temperature. Detailed computational studies support the formation of a key intermediate and are also in agreement with a rapid carbonylation/decarbonylation reaction. The computed reactions mechanisms for addition of PPA-HCl and CA are also presented as well as the crystal structure of 1.



中文翻译:

Au(I)的N-杂环卡宾配合物使炔丙基胺羧化环化的机理。

 由[Au(IPr)Cl](2),K 2 CO 3和炔丙基胺(PPA)的反应制备[Au(IPr)(2-恶唑烷酮)]络合物(1= IKa )。进行了1酸裂解的动力学研究,得到了恶唑烷酮产物和[Au(IPr)(X)]加合物。发现最快的裂解速率发生在PPA的氯化氢盐(PPA-HCl)和PPA的CO 2加合物中,PPA-CO 2  =氨基甲酸(CA)。研究了这种转变与[CA],CO 2压力的关系。以及温度。详细的计算研究支持关键中间体的形成,并且也与快速的羰基化/脱羰基反应一致。还介绍了计算的添加PPA-HCl和CA的反应机理,以及1的晶体结构。

更新日期:2020-10-19
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