Multi-functionalized tertiary/secondary boronates and silanes have found wide applications in areas spanning organic synthesis, advanced material development, and pharmaceutical research. Effective access to these versatile motifs via protoboration/silylation of allenes remains unfulfilled. Capitalizing on the fluorine effects, here we report copper-catalyzed protoboration/silylation of gem-difluoroallenes, which shows an abnormal reactivity profile. In stark contrast to the conventional paradigms of allene functionalization reactions, which are often subjected to the steric-control mode for more facile reaction initiation on lower-substituted double bonds, the present reaction displays a virtually reversed regioselectivity for the more sterically congested π system. The synergistic LUMO-lowering perturbation and stabilization of nascent organocopper by fluorine substituents are deemed critical for guaranteeing the high fidelity of the present transformation. We not only apply this developed methodology to the late-stage modification of compounds derived from natural products but also highlight the utility of the obtained gem-difluoroalkenes in further synthetic elaborations.

多功能三级/二级硼酸酯和硅烷在有机合成、先进材料开发和药物研究等领域得到广泛应用。通过丙二烯的原硼化/硅烷化有效地获得这些多功能基序仍未实现。利用氟效应，我们在这里报告了铜催化的宝石原硼化/硅烷化-二氟丙二烯，显示出异常的反应性。与丙二烯官能化反应的传统范式形成鲜明对比，传统范式通常采用空间控制模式，以便在较低取代的双键上更容易地引发反应，而本反应对空间更拥挤的 π 系统显示出实际上相反的区域选择性。氟取代基对新生有机铜的协同降低 LUMO 扰动和稳定化被认为是保证当前转化的高保真度的关键。我们不仅将这种开发的方法应用于源自天然产物的化合物的后期改性，而且还强调了所获得的gem-二氟烯烃在进一步合成过程中的效用。