ABSTRACT
A polarity-reversing radical cascade strategy for alkene di-functionalization by vicinal C-C and C-P bond-formation has been developed. This approach to concurrently adding phosphorous and a heteroarene across an olefin is enabled by photocatalytic generation of electrophilic P-centered radicals. Upon chemoselective addition to an olefin, the resulting nucleophilic C-centered radical selectively combines with electrophilic heteroarenes, such as pyridines. This multi-component coupling scheme for phosphinylalkylation complements classic two-component methods for hydrophosphinylation of alkenes and C-H phosphinylation of arenes. Included competition and photo-quenching experiments provide insight into the selectivity and mechanism of this polarity-reversal pathway.
ABSTRACT
A multi-component radical addition strategy enables difunctionalization of alkenes with heteroarenes and a variety of radical precursors, including N3, P(O)R2, and CF3. This unified approach for coupling diverse classes of electrophilic radicals and heteroarenes to vinyl ethers allows for direct, vicinal C-C as well as C-N, C-P, and C-Rf bond formation.