Selective sulfonylation and isonitrilation of para-quinone methides employing TosMIC as a source of sulfonyl group or isonitrile group

Chemoselective sulfonylation and isonitrilation reactions for the divergent synthesis of valuable diarylmethyl sulfones and isonitrile diarylmethanes starting from easy-to-synthesize para-quinone methides (p-QMs) and commercially abundant p-toluenesulfonylmethyl isocyanide (TosMIC) by using respectively zinc iodide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as catalysts were developed. The distinguishing feature of this method is that TosMIC plays a dual role from the same substrates in the reaction: as a sulfonyl source or as an isonitrile source. The synthetic utility of this protocol was also demonstrated in the synthesis of difluoroalkylated diarylmethane 5 and diarylmethane ketone derivatives 6 and 7, which are important core structures in natural products and medicines.

Photoinduced C(sp3)–H Sulfination Empowers a Direct and Chemoselective Introduction of the Sulfonyl Group

Direct installation of the sulfinate group by a functionalization of unreactive aliphatic C–H bonds can provide an entry to most classes of organosulfur compounds, because of the central position of...

Preparation of 1,2-substituted benzimidazoles via a copper-catalyzed three component coupling reaction

The intermediate N-sulfonylketenimine occurred with two nucleophilic addition, and the sulfonyl group was easily eliminated through cyclization.

Sulfonamide Directivity Enables Ni-Catalyzed 1,2-Diarylation of Diverse Alkenyl Amines

1,2-Diarylation of alkenyl sulfonamides with aryl iodides and aryl boronic esters under nickel catalysis is reported. The developed method tolerates coupling partners with disparate electronic properties and substitution patterns. 1,2- and 1,1-Disubstituted alkenes, as well as alkenes distal from the directing group, are all accommodated. Control experiments are consistent with a N–Ni coordination mode of the directing group, which stands in contrast to earlier reports on amide-directed 1,2-diarylation that involve carbonyl coordination. The synthetic utility of the method arises from the dual function of the sulfonamide as both a directing group and masked amine nucleophile. This is highlighted by various product diversifications where complex amine compounds are synthesized in a two-step sequence of <i>N</i>-functionalization and deprotection of the sulfonyl group.

Sulfonamide Directivity Enables Ni-Catalyzed 1,2-Diarylation of Diverse Alkenyl Amines

1,2-Diarylation of alkenyl sulfonamides with aryl iodides and aryl boronic esters under nickel catalysis is reported. The developed method tolerates coupling partners with disparate electronic properties and substitution patterns. 1,2- and 1,1-Disubstituted alkenes, as well as alkenes distal from the directing group, are all accommodated. Control experiments are consistent with a N–Ni coordination mode of the directing group, which stands in contrast to earlier reports on amide-directed 1,2-diarylation that involve carbonyl coordination. The synthetic utility of the method arises from the dual function of the sulfonamide as both a directing group and masked amine nucleophile. This is highlighted by various product diversifications where complex amine compounds are synthesized in a two-step sequence of <i>N</i>-functionalization and deprotection of the sulfonyl group.