Intramolecular “Hydroiminiumation and -amidiniumation” of Alkenes: A Convenient, Flexible, and Scalable Route to Cyclic Iminium and Imidazolinium Salts

Addition of a stoichiometric amount of HCl to alkenylaldimines, -formamidines, and -amidines results
in the protonation of the sp2-nitrogen atom. The resulting alkenylaldiminium, -formamidinium, and
-amidinium salts can be isolated and fully characterized, including single-crystal X-ray diffraction studies.
Heating solutions of these salts induces ring closure cleanly and regioselectively via formal “exo” addition
of the nitrogen−hydrogen bond to the pendent carbon−carbon double bond, affording the corresponding
cyclic aldiminium, dihydroisoquinolinium, and imidazolinium salts. Of special interest, novel 4,4-disubstituted imidazolinium salts are accessible via this synthetic route. Similarly, addition of phosgene
to alkenyl ureas and alkenyl amides, followed by gentle heating, cleanly affords C-chloro imidazolinium,
and cyclic C-chloro iminium salts, respectively. Treatment of the latter with tetrakis(triphenylphosphine)palladium allows for the preparation of the first transition-metal complex bearing a cyclic arylaminocarbene
as ligand. Deuterium labeling experiments suggest that the mechanism of the hydroiminiumation and
-amidiniumation reactions involves an intramolecular proton transfer to the double bond in the rate-determining step. This novel synthetic methodology gives access to a variety of N-heterocyclic carbene
(NHC) and cyclic alkyl- and arylaminocarbene (CAAC) precursors.