Two flavors of PEPPSI-IPr: activation and diffusion control in a single NHC-ligated Pd catalyst?
摘要：
Abnormal reactivity has been observed in Negishi, Suzuki-Miyaura, and Kumada-Tamao-Corriu cross-couplings in which PEPPSI-(where PEPPSI stands for enhanced precatalyst preparation, stabilization, and initiation and refers to the ligand) is employed, implicating the presence of two distinct Pd(0) species in the catalytic cycle. Polybrominated and organometallic reagents react selectively to give the product of exhaustive polysubstitution regardless of the initial reaction stoichiometry. Competition experiments suggest that, after an initial activation controlled oxidative addition, reductive elimination produces an ultrareactive Pd(0) species which consumes all remaining C-Br bonds in the molecule under diffusion control.
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DOI：
10.1021/ol1027283
被引量：
年份：
2011
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