Chemodivergent dehydrative nucleophilic substitutions of diarylmethanols with 1‐phenyl‐1H‐tetrazole‐5‐thiol were achieved using FeCl3 as a catalyst in MeNO2 by changing reaction temperature. It was found that sulfur nucleophilic attack occurred to afford kinetically controlled products that rearranged into thermodynamically controlled products. A variety of diarylmethanols could be applied to the reaction, irrespective of the substituents on the aromatic rings of the substrates. It was also revealed that the reactions of several kinds of alkyl‐ and heteroaryl‐substituted benzyl alcohols gave moderate to good product yields. The controlled experiments performed revealed that both reactions proceeded in an SN1 fashion and heating with a Lewis acid was necessary for rearrangement.

Nucleophilic substitutions of benzylic alcohols with sulfamides were achieved using an FeCl 3 Lewis acid catalyst in MeNO 2 . It was necessary to adjust the reaction conditions to obtain efficient yields depending on the stability of the carbocation intermediates. The reaction could easily be performed, and it [a

The FeCl 3 -catalyzed, diastereodivergent sulfamidation of diastereomixtures of diarylmethanols bearing a chiral auxiliary was achieved and was found to be dependent on the catalyst loading. Under these conditions, a variety of substrates bearing different substituents on their aromatic rings could be applied to both reaction pathways. The sulfamide moieties were easily removed to give the corresponding chiral amines. Chiral sulfamides with different stereochemistry were efficiently synthesized as organocatalysts using the present method.