A Desulfonylative Approach in Oxidative Gold Catalysis: Regiospecific Access to Donor‐Substituted Acyl Gold Carbenes
作者:Hongyi Chen、Liming Zhang
DOI:10.1002/anie.201504511
日期:2015.9.28
Donor‐substituted acyl gold carbenes are challenging to access selectively by gold‐promoted intermolecular oxidation of internal alkynes as the opposite regioisomers frequently predominate. By using alkynyl sulfones or sulfonates as substrates, the oxidative gold catalysis in the presence of substituted pyridine N‐oxides offers regiospecific access to acyl/aryl, acyl/alkenyl, and acyl/alkoxy gold carbenes
供体取代的酰基金卡宾因通过金促进内部炔烃的分子间氧化而选择性地进入具有挑战性,因为相反的区域异构体通常占主导地位。通过使用炔基砜或磺酸盐作为底物,在取代的吡啶N-氧化物存在下的氧化金催化作用可通过原位排出二氧化硫,使区域特异性地接近酰基/芳基,酰基/烯基和酰基/烷氧基金羰基。这些反应性物种的中间性是由它们的反应性决定的,包括通过相同的氧化剂进行进一步的氧化,苯乙烯的环丙烷化,与α-甲基苯乙烯的[3 + 2]环加成反应以及转化为二烯酮。