Rhodium(II)-Catalyzed Alkynyl Carbene Insertion into N-H Bonds.

The first insertion of an alkynyl carbene into N-H bonds under Rh-catalysis is developed. Alkynyl hydrazone carboxylates are used as donor-acceptor carbene precursors and are exquisitely inserted into the N-H bonds of various amines, amides, and 1,2-diamines. A wide variety of 3-alkynyl 3,4-dihydroquinoxalin-2(1H)-ones and densely functionalized α-alkynyl α-amino esters are obtained in good to excellent yields. Further, chemoselective N-H insertion reactions, mechanistic studies, and various synthetic transformations for obtaining valuable heterocycles are demonstrated.

Doyle-Kirmse Reaction on Alkynyl Hydrazone Carboxylates: Synthesis of 1,4-Allenyne and 1,5-Enyne Thioaryl Carboxylates.

The first Doyle-Kirmse reaction on alkynyl diazoacetates using allyl/propargyl sulfides is reported. The development provides diversified 1,5-enyne and 1,4-allenyne thioaryl carboxylates in good yields under ligand-/additive-free AuCl and Rh2(OAc)4 catalysis, respectively (48 examples, up to 96% yield). The study demonstrated the dual role of allyl sulfide as a ligand and substrate. Also, we have exemplified various synthetic modifications of the products to showcase the utility of different functional groups.

Synthesis of Alkynyl Hydrazones from Unprotected Hydrazine and Their Reactivity as Diazo Precursors.

Alkynyl hydrazones are synthesized conveniently from 2-oxo-3-butynoates and hydrazine by suppressing the susceptible formation of pyrazoles. The resultant hydrazones are transformed into alkynyl diazoacetates under metal-free and mild oxidative conditions in excellent yields. Further, the alkynyl cyclopropane and propargyl silane carboxylates are synthesized in good yields by developing an unprecedented copper-catalyzed alkynyl carbene transfer reaction.