A novel, mild and practical protocol for the efficient activation of the Beckmann rearrangement utilizing the readily available and economical sulfuryl fluoride (SO 2 F 2 gas) has been developed. The substrate scope of the operationally simple methodology has been demonstrated by 37 examples with [a]

The first example of silver-mediated phosphine-promoted methoxylation of aryl C(sp2)–H bonds with the commercially available reagent for the preparation of alkyl aryl ethers has been developed. This protocol is characterized by mild reaction conditions, broad substrate scope, and high regioselectivity.

A novel SO2F2-promoted thiocyanation method for the one-step synthesis of thiocyanates through C–O bond cleavage of readily available alcohols with ammonium thiocyanate as the thiocyanating agent was developed. The method avoids the use of additional catalyst, and a variety of (hetero)arene, alkene and aliphatic alcohols reacted with high efficiency in ethyl acetate under mild conditions to afford the corresponding thiocyanates in excellent to quantitative yields with broad functional-group compatibility.