Nucleophilic β-Oniovinylation: Concept, Mechanism, Scope, and Applications

Insertion of an electron-deficient alkyne A−C⋮C−A (A = CO2Me) into the C−L+ bond of an
acyl-onio salt R−C(O)−L+ (R = Ar, OAlk; L = 4-dimethylaminopyridine, PPh3) has for the first time been
achieved in the presence of catalytic amounts of the nucleophile L. For R = OMe, a second insertion of
the alkyne was observed. X-ray structures were obtained for a number of such β-oniovinylation products.
Depending on reaction conditions, preferentially E- or Z-stereochemistry was observed, the Z-isomer being
the thermodynamically more stable. A mechanism for this novel insertion reaction is presented which
accounts for the topology of the products and rationalizes the observed stereochemistry. The β-onio-activated
Michael systems thus generated represent a virtually unexplored class of compounds. The onio substituent
in such compounds can be selectively replaced by a number of nucleophiles. Thus a series of Michael
systems with donor functions in the β-position is easily synthesized. These compounds represent a source
for useful further transformations, for example, cyclizations to quinolones, thiochromones, and pyrazoles.