LAUSR

The potent nucleophilicity and remarkably low basicity of 1,3,2‐diazaphospholenes (DAPs) is exploited in a catalytic, metal‐free 1,4‐reduction of free α,β‐unsaturated carboxylic acids. Notably, the reduction occurs without a prior deprotonation of the carboxylic acid moiety and hence does not consume an additional hydride equivalent. This highlights the excellent nucleophilic character and low basicity of DAP‐hydrides. Functional groups such as Cbz group or alkyl halides which can be problematic with classical transition‐metal catalysts are well tolerated in the DAP‐catalyzed process. Moreover, the transformation is characterized by a low catalyst loading, mild reaction conditions at ambient temperature as well as fast reaction times and high yields. The proof‐of‐principle for a catalytic enantioselective version is described.