Computational Mechanistic Study of Stereoselective Suzuki Coupling of an α-Cyano-Activated Secondary Alkyl
作者： Bimal Pudasaini , Benjamin G. Janesko
DOI: 10.1021/OM300455G
关键词:
摘要: Palladium-catalyzed cross-couplings of secondary alkyls are promising tools for the stereoselective formation carbon–carbon bonds. We report a computational mechanistic study Suzuki coupling between (S)-2-chloropropanenitrile and phenylboronic acid, following recent experimental on related α-cyanohydrin triflates (J. Am. Chem. Soc. 2010, 132, 2524). Added Lewis base helps accelerate SN2 oxidative addition, leading to experimentally observed inversion configuration. Undesired β-hydride elimination side reactions reduced by activating cyano group’s inductive effects, cyano-PdII coordination, excess boronic acid. The catalyst ligand’s trans influence steric bulk also affect rate elimination, suggesting design rules alkyl cross-coupling ligands.
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