Illuminating Iron Catalyst with Blue Light: Efficient Access to <i>N</i> -alkylated Phosphinic (Thio)amides

A sustainable approach for the N-alkylation of phosphinic amides and phosphinic thioamides using (bio)alcohols as electrophilic partners has been developed by using an iron catalyst. This catalytic system enables efficient hydrogen borrowing transformation under blue-light irradiation, under ambient conditions, with water as the sole byproduct. The method exhibits a broad functional group tolerance, affording N-alkylated phosphinic (thio)amide derivatives in moderate to good yields (43 examples, up to 99% yields). Noticeably, experimental evidence supports the proposed mechanism.