A highly regioselective and catalyst-free sulfonation of allylic alcohols with sulfinyl amides has been realized. Such a mix-and-go procedure provides a convenient approach to synthetically various allylic sulfones under mild reaction conditions. Furthermore, this novel reaction shows ample substrate scope and outstanding functional group tolerance and could also be scaled-up. Meanwhile, it is the first example that sulfinyl amides act as a powerful sulfur nucleophile in the reactions. 1,1,1,3,3,3-Hexafluoro-2-propanol (HFIP) as a solvent plays a critical role in allylic sulfonation.

The rhodium(III)-catalyzed aryl borrowing amination of various diaryl methanols with sulfonamides have been developed. The amination of alcohols via CÀ C bond activation is less developed and remains a challenge. These aryl borrowing reactions feature mild reaction conditions, good functional group tolerance, and compatibility with a wide range of alcohols, overall comprising an atom-and step-economic procedure. Mechanistic studies indicate that a rhodacycle complex exist during the aryl borrowing amination reaction.

A regio-and chemoselective sulfonylation of propargyl alcohols with sulfinamides in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) was developed. It provided straightforward and mild access to multi-substituted allenyl sulfones by using sulfinamides as the sulfonyl sources. This transformation was promoted by HFIP and did not require any catalysts or oxidants, which allowed for the successful conversion of various tertiary and secondary propargyl alcohols into allenyl sulfones in high yields.

The isomerization of allylic alcohols to the corresponding carbonyl compounds is a well-established reaction in organic synthesis. However, 1,3-carbon migration is a quite challenging field, and thus transformation has remained elusive until now. Herein, we present the ruthenium-catalyzed intramolecular 1,3-aryl migrative isomerization, which provides a mild and environmentally friendly method to synthesize various ketones with high step-and atom-economy and broad substrate scope. Meanwhile, the Ru(III)-catalyzed C(sp 3 )−C(aryl) bond cleavage of unactivated allylic alcohols may serve as a heuristic paradigm for transition-metal-catalyzed C−C activation.

2-Pyridinylmethyl Borrowing: Transition-metal-free 2-pyridinylmethyl borrowing C-alkylation of alcohols access to ketones is developed. This unstrained C(sp3)–C(sp3) bonds cleavage of unactivated alcohols avoids the use of transition metals.