We report a method for the synthesis of carbamoyl fluorides from secondary amines using bench-stable, inexpensive, and readily accessible starting materials that, when combined, yield a surrogate for toxic difluorophosgene (COF 2 ) gas. In contrast to state-of-the-art methods for the synthesis of carbamoyl fluorides, our protocol does not require the use of pre-functionalized substrates, the preparation of light-, temperature-, and/or moisture-sensitive chemicals, or the application of explosive fluorinating reagents.

Due to the unique properties of C−F bonds, organofluorine compounds occupy a privileged space in the pharmaceutical, agrochemical, and polymer industries. Carbofluorination reactions involve the formation of a C−C and a C−F bond, typically across a π‐bond or another unsaturated functionality that is revealed upon in situ activation. The design of tailored substrates and new catalyst systems has enabled carbofluorination chemistry to emerge as a promising manifold for the synthesis of unique fluorinated scaffolds. This review covers the application of nucleophilic and electrophilic fluorinating reagents in this chemistry, in addition to recently developed atom‐economical carbofluorination reactions using organofluorine compounds as dual reagents.

A pair of ortho-benzoate esters containing epimeric pyrroloimidazolones undergo sequential Birch reduction and diastereoselective alkylation to provide products ranging from 88:12 to >95:5 diastereomeric ratio (dr) for the syn-epimer, and 50:50 to 95:5 dr for the anti-epimer. The stereochemistry of the products is confirmed by a combination of X-ray crystallography on a key anti-epimer-derived product, in combination with specific rotation measurements of enantiomers that are prepared from the syn or anti starting materials. A diastereomerically pure allyl-substituted substrate is shown to undergo Cope rearrangement, which transposes the quaternary chiral center to a remote position without racemization. This work is complementary to asymmetric reductive alkylation reported previously by Schultz using anisole substrates with chiral benzamide auxiliaries in that the pyrroloimidazolones act as surrogates for the methoxy group.