The introduction of allyl fluorides as alternative electrophiles in asymmetric allylic alkylation reactions has recently attracted significant interest. Despite the intrinsic thermodynamically demanding C–F bond-cleavage event, the fluorophilic nature of the silicon atom is key in assisting the activation and cleavage of the allylic C–F bond. Thus, the use of silylated compounds as unconventional nucleophiles, together with the Lewis basicity of fluorine when acting as a leaving group, enables the development of innovative chemical transformations within mild and selective catalytic schemes. This Synpacts article summarizes the diverse defluorinative asymmetric allylic alkylations with allyl fluorides reported to date under both chiral Lewis base and transition-metal catalysis.

在不对称烯丙基烷基化反应中引入烯丙基氟作为替代亲电子试剂最近引起了人们的极大兴趣。尽管存在内在的热力学要求的 C-F 键断裂事件，但硅原子的亲氟性质是协助烯丙基 C-F 键激活和断裂的关键。因此，使用硅烷化化合物作为非常规亲核试剂，加上氟作为离去基团时的路易斯碱性，使得能够在温和和选择性的催化方案中开发创新的化学转化。这篇 Synpacts 文章总结了迄今为止在手性路易斯碱和过渡金属催化下报道的各种烯丙基氟化物脱氟不对称烯丙基烷基化反应。