Ab road-spectrum, catalytic method has been developed for the synthesis of sulfonamides and sulfamates. With the activation by the combination of acatalytic amount of 1-hydroxybenzotriazole(HOBt) and silicon additives,amidations of sulfonyl fluorides and fluorosulfates proceeded smoothly and excellent yields were generally obtained (87-99 %). Noticeably,t his protocol is particularly efficient for sterically hindered substrates.Catalyst loading is generally low and only 0.02 mol %o fc atalyst is required for the multidecagram-scale synthesis of an amantadine derivative.Inaddition, the potential of this method in medicinal chemistry has been demonstrated by the synthesis of the marketed drug Fedratinib via ak ey intermediate sulfonyl fluoride 13.S ince al arge number of amines are commercially available,t his route provides af acile entry to access Fedratinib analogues for biological screening.

Annulations of ortho-phosphinoarenesulfonyl fluorides with trimethylsilyl azide were developed to access an unprecedented benzo-1,2,3-thiazaphosphole heterocycle. A corresponding reaction mechanism was proposed and further elucidated by experimental and computational studies. The reaction proceeds through a Staudinger-type iminophosphorane intermediate followed by intramolecular trapping with sulfonyl fluoride.

A broad‐spectrum, catalytic method has been developed for the synthesis of sulfonamides and sulfamates. With the activation by the combination of a catalytic amount of 1‐hydroxybenzotriazole (HOBt) and silicon additives, amidations of sulfonyl fluorides and fluorosulfates proceeded smoothly and excellent yields were generally obtained (87–99 %). Noticeably, this protocol is particularly efficient for sterically hindered substrates. Catalyst loading is generally low and only 0.02 mol % of catalyst is required for the multidecagram‐scale synthesis of an amantadine derivative. In addition, the potential of this method in medicinal chemistry has been demonstrated by the synthesis of the marketed drug Fedratinib via a key intermediate sulfonyl fluoride 13. Since a large number of amines are commercially available, this route provides a facile entry to access Fedratinib analogues for biological screening.

An alternative scalable process for the synthesis of the key intermediate of omarigliptin is described. The asymmetric synthesis relies on the initial diastereoselective alkylation and subsequent aluminum-catalyzed substrate-controlled Meerwein−Ponndorf−Verley reduction. A highly regioselective 5-exo-dig iodocyclization followed to afford 11b, which was then subjected to ring-opening cycloetherification to give product 1 with >99:1 dr and >99% ee in 31.2% overall yield in nine steps. This synthetic strategy has been successfully applied for multikilogram scale production.