Alvarez Rosana, Faza Olalla Nieto, López Carlos Silva, de Lera Angel R
Departamento de Química Orgánica, Universidade de Vigo, Lagoas-Marcosende, Spain.
Org Lett. 2006 Jan 5;8(1):35-8. doi: 10.1021/ol052398f.
[reaction: see text] The species presumably involved in the associative ligand substitution mechanism for the Stille cross coupling of vinyl bromide and trimethylvinyl stannane with Pd(PMe(3))(2)/PMe(3) as catalysts in DMF (as ligand and solvent) have been structurally and energetically characterized. The cyclic four-coordinate transition state for the rate-determining transmetalation step explains the retention of configuration in the Stille coupling of chiral nonracemic alkyl stannanes.
[反应：见正文] 据推测，在以Pd(PMe(3))(2)/PMe(3)为催化剂、DMF（作为配体和溶剂）中进行溴乙烯与三甲基乙烯基锡的Stille交叉偶联的缔合配体取代机理中所涉及的物种，已通过结构和能量进行了表征。速率决定的金属转移步骤的环状四配位过渡态解释了手性非外消旋烷基锡在Stille偶联中构型的保留。
