The Direct Rh(III)-Catalyzed C-H Amidation of Aniline Derivatives Using a Pyrimidine Directing Group: The Selective Solvent Controlled Synthesis of 1,2-Diaminobenzenes and Benzimidazoles.

The regioselective Rh(III)-catalyzed C-H amidation of aniline derivatives with dioxazolones as an amidating reagent with a pyrimidine as a directing group leading to the production of 1,2-diaminobenzene derivatives or benzimidazole derivatives is described. The product distribution is controlled by the nature of solvent used. The reaction provides a broad substrate scope for aniline derivatives with various important functional groups including dioxazolones.

A General Nickel-Catalyzed Method for C-H Bond Alkynylation of Heteroarenes Through Chelation Assistance.

A general nickel-catalyzed method for the alkynylation of heteroarenes through monodentate chelation assistance is described. Many heterocycles, including indoles, pyrroles, imidazoles, and pyrazole, efficiently coupled with (triisopropylsilyl)alkynyl bromide, and synthetically important functional groups, such as halides, ether, nitrile, and nitro, are tolerated. Synthetic applicability of this Ni-catalyzed method is demonstrated by the removal of the triisopropylsilyl group and further functionalization to triazolyl, benzofuranyl, and alkynyl arene derivatives.

Design and development of POCN-pincer palladium catalysts for C-H bond arylation of azoles with aryl iodides.

Well-defined and efficient POCN-ligated palladium complexes have been developed for the direct C-H bond arylation of azoles with aryl iodides. The phosphinite-amine pincer ligands 1-(R2PO)-C6H4-3-(CH2N(i)Pr2) [(R2)POCN(iPr2)-H; R = (i)Pr (), R = (t)Bu ()] and corresponding palladium complexes {2-(R2PO)-C6H3-6-(CH2N(i)Pr2)}PdCl [((R2)POCN(iPr2))PdCl; R = (i)Pr (), R = (t)Bu ()] were synthesized in good yields. Treatment of palladium complex with KI and AgOAc afforded the complexes ((iPr2)POCN(iPr2))PdI () and ((iPr2)POCN(iPr2))Pd(OAc) (), respectively.