Substituent Effects and the Mechanism of Gold to Alkene Benzylidene Transfer Employing a Gold Sulfonium Benzylide Complex
作者:Mitch Rivers、Robert G. Carden、Ross A. Widenhoefer
DOI:10.1021/acs.organomet.2c00097
日期:2022.5.9
sulfonium benzylide complex [(P)AuCHPh(SPh2)]+ B [3,5-CF3C6H3]4}− [P = P (t-Bu)2o-biphenyl; 1] at room temperature via the cationic two-coordinate gold benzylidene complex [(P)AuCHPh]+ (I) to form phenyclyclopropanes. The reactivity of p-substituted vinyl arenes toward I decreased with the decreasing electron donor ability of the vinyl arene (ρ = −1.49 ± 0.15), and the reactivity of aliphatic alkenes
脂肪族和芳香族烯烃与金锍苄基络合物 [( P )AuCHPh(SPh 2 )] + B [3,5-CF 3 C 6 H 3 ] 4 } - [ P = P ( t -Bu ) 2邻联苯;1 ] 在室温下通过阳离子双配位金亚苄基配合物[( P )AuCHPh] + ( I ) 生成苯环丙烷。对位取代乙烯基芳烃对I的反应性随着乙烯基芳烃的电子供体能力降低(ρ = -1.49 ± 0.15),脂肪族烯烃对I的反应性在很大程度上取决于连接到更多取代烯烃末端的烷基数量。亚苄基向顺式和反式-β-甲基苯乙烯的转移发生,烯烃构型完全保留。亚苄基转移到乙烯基芳烃导致顺式的主要形成-环丙烷(dr = 4.1:1 至 13.9:1),而亚苄基转移至脂肪族烯烃的选择性通常较低(dr = 1.3:1 至 5.1:1)。我们所有的实验观察结果都与协调的、异步的、亲电的亚苄基转移机制一致。亚苄基转移的非对映选择性是在