Gold Sulfonium Benzylide Complexes Undergo Efficient Benzylidene Transfer to Alkenes
Gold Sulfonium Benzylide Complexes Undergo Efficient Benzylidene Transfer to Alkenes
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DOI：
10.1002/chem.201902845
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发表时间：
2019-07-26
影响因子：
4.3
通讯作者：
Widenhoefer, Ross A.
中科院分区：
文献类型：
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作者：
Carden, Robert G.;Widenhoefer, Ross A.
金锍苯甲酰配合物 [(P1)AuCHPh((SRR2)-R-1)](+) {B[3,5-CF3C6H3](4)}(-) [P1=P(tBu)(2)o-联苯； R-1、R-2=-(CH2)(4)-(1a)； R-1=Et，R-2=Ph (1b)； R-1=R-2=Ph (1 c)]通过金α-氯苄基络合物(P1)AuCHClPh与四[3,5-双(三氟甲基)苯基]硼酸钠和过量的硫化物反应合成。配合物 1 在温和条件下无需外部活化即可有效地进行亚苄基转移至烯烃和 DMSO。 1 c 与苯乙烯反应的动力学分析与阳离子金亚苄基配合物 [(P1)AuCHPh](+) (I) 的中介作用一致。
The gold sulfonium benzylide complexes [(P1)AuCHPh((SRR2)-R-1)](+) {B[3,5-CF3C6H3](4)}(-) [P1=P(tBu)(2)o-biphenyl; R-1, R-2=-(CH2)(4)- (1 a); R-1=Et, R-2=Ph (1 b); R-1=R-2=Ph (1 c)] were synthesized by reaction of the gold alpha-chloro benzyl complex (P1)AuCHClPh with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and excess sulfide. Complexes 1 undergo efficient benzylidene transfer to alkenes and DMSO under mild conditions without external activation. Kinetic analysis of the reaction of 1 c with styrene was consistent with the intermediacy of the cationic gold benzylidene complex [(P1)AuCHPh](+) (I).