The electrochemical synthesis of fluorinated allyl silanes and boronates was disclosed. The addition of electrogenerated boryl or silyl radicals onto many α‐trifluoromethyl or α‐difluoromethylstyrenes in an undivided cell allowed the formation of a large panel of synthetically useful gem‐difluoro and γ‐fluoroallyl boronates and silanes (64 examples, from 31 % to 95 % yield). In addition, a scale up of the reactions under continuous flow was showcased using an electrochemical reactor with promising volumetric productivity (688 g.L−1.h−1 and 496 g.L−1.h−1). Moreover, the synthetic utility of these building blocks was highlighted through versatile transformations. Finally, plausible reaction mechanisms were suggested to explain the formation of the products.

Herein, the electrochemical hydrosilylation of alkynes is reported. In the presence of the Suginome reagent (PhMe 2 Si− Bpin), a large panel of terminal alkynes and internal alkynes was successfully converted into the hydrosilylated product in good to excellent yields and good selectivity in favor of the linear product. Preliminary mechanistic study supported the involvement of a silyl radical, which reacted on the alkyne.