A novel catalytic hydrogen-autotransfer protocol for the atom-efficient α-alkylation of ketones with readily available alcohols is presented. The use of manganese complexes bearing non-innocent PNP pincer ligands enabled the functionalization of a broad range of valuable ketones, including 2-oxindole, estrone 3-methyl ether, and testosterone. Mechanistic investigations suggest the participation of an intramolecular amidate-assisted alcohol-dehydrogenation process.

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The palladium-catalyzed cross-coupling reaction of organogold(I) reagents (alkyl, alkenyl, aryl, and alkynyl) with organic electrophiles, such as aryl and alkenyl halides, aryl triflates, benzyl bromide, and benzoyl chloride is reported. The reaction takes place, under palladium catalysis, at room temperature with short reaction times to give the corresponding cross-coupling products in high yields.

The synthesis of lactones and lactams by using iron(II) pincer‐catalyzed dehydrogenative methodology was developed. Starting from 1,n‐diols or 1,n‐amino alcohols, this domino transformation takes place through initial dehydrogenation of the substrates, subsequent intramolecular cyclization, and final oxidation to afford the desired products in good yields. The ability to access heterocycles of different sizes makes this protocol especially versatile, in which two consecutive oxidation reactions are performed without requiring an external oxidant. In this paper, we report the application of the Fe‐MACHO‐BH complex [carbonylhydrido(tetrahydroborato)[bis(2‐diisopropylphosphinoethyl)amino]iron(II)] in this atom‐efficient and environmentally benign process, for which molecular hydrogen is formed as the only stoichiometric side product.

A novel rhenium complex bearing a non-innocent PNP pincer ligand was prepared. This novel catalyst is active in hydrogen autotransfer reactions to form new C-C and C-N bonds. More specifically, valuable alkylations of ketones and sulfonamides with primary alcohols are herein presented. In addition, the first examples of rhenium-catalysed synthesis of pyrroles are described by dehydrogenative coupling of diols, amines and ketones.