Nickel-catalyzed C-O/N-H, C-S/N-H, and C-CN/N-H annulation of aromatic amides with alkynes: C-O, C-S, and C-CN activation.

The Ni-catalyzed reaction of ortho-phenoxy-substituted aromatic amides with alkynes in the presence of LiO t Bu as a base results in C-O/N-H annulation with the formation of 1(2H)-isoquinolinones. The use of a base is essential for the reaction to proceed. The reaction proceeds, even in the absence of a ligand, and under mild reaction conditions (40 °C). An electron-donating group on the aromatic ring facilitates the reaction. The reaction was also applicable to carbamate (C-O bond activation), methylthio (C-S bond activation), and cyano (C-CN bond activation) groups as leaving groups.

Nickel-catalyzed reductive defunctionalization of esters in the absence of an external reductant: activation of C-O bonds.

The nickel-catalyzed reductive cleavage of esters in the absence of an external reductant, which involves the cleavage of an inert acyl C-O bond in O-alkyl esters is reported. Various groups, such as N-containing heterocycles, esters, amides, and even arene rings can function as a directing group.

Conversion of 3,3,3-Trisubstituted Prop-1-ynes with tert-Butylhydrazine into 3,3,3-Trisubstituted Propionitriles Catalyzed by TpRh(C2H4)2/P(2-furyl)3.

The combination of TpRh(C2H4)2 (Tp = tris(pyrazol-1-yl)borate) and P(2-furyl)3 catalyzes the reaction of tertiary alkyl-substituted alkynes with tert-butylhydrazine, leading to the formation of 3,3,3-trisubstituted propionitrile derivatives. This reaction system is applicable to 1,1-disubstituted propargyl alcohols and amines to afford the corresponding ß-cyanohydrins and ß-amino nitriles, respectively. The catalytic cycle involves the formation of a vinylidenerhodium complex as a key intermediate.