Trifluoromethylfluorosulfonylation of Unactivated Alkenes Using Readily Available Ag(O₂CCF₂SO₂F) and N‐Fluorobenzenesulfonimide

Abstract

Presented is a novel intermolecular radical trifluoromethylfluorosulfonylation of unactivated alkenes under mild reaction conditions with good functional-group tolerance in the most atom-economic manner by using readily available Ag(O CCF SO F) and N-fluorobenzenesulfonimide (NFSI). Both the trifluoromethyl and sulfonyl groups in the products originate from Ag(O CCF SO F).

Trifluoromethanesulfonic Anhydride as a Low‐Cost and Versatile Trifluoromethylation Reagent

“…Among the developed radical trifluoromethylation methods, photoredox‐ or transition‐metal‐catalyzed radical trifluoromethylation has received great attention recently. In this context, a large number of trifluoromethylation reagents have been recognized as the trifluoromethyl radical precursors, including CF 3 X (X=I, Br), CF 3 CO 2 H and its derivatives, CF 3 SO 2 ‐containing compounds (CF 3 SO 2 Na, Zn(SO 2 CF 3 ) 2 , [CF 3 SO 2 Ag], CF 3 SO 2 Cl, triflones), TMSCF 3 , Umemoto reagent, and Togni reagent . However, most of them are either expensive (Zn(SO 2 CF 3 ) 2 , Umemoto and Togni reagents), commercially unavailable ([CF 3 SO 2 Ag], triflones), gaseous (CF 3 I, CF 3 Br), or volatile (CF 3 SO 2 Cl, TMSCF 3 ), which significantly restricts their widespread application.…”

Trifluoromethylfluorosulfonylation of Unactivated Alkenes Using Readily Available Ag(O2CCF2SO2F) and N‐Fluorobenzenesulfonimide

“…Yield [%] [b] 1C [c] Yields were determined by 19 FNMR spectroscopy with 1-methoxy-4-(trifluoromethoxy)benzene as an internal standard. Thermal ellipsoids of the X-ray crystal structure [15] of 2u shown at 50 %probability.…”

Evidence of Phosphonium‐Carbenium Dication Formation in a Superacid: Precursor to Fluorinated Phosphine Oxides

“…Organophosphorus compounds have found wide application in various fields such as catalysis, medicinal chemistry, material science and inorganic chemistry . To our knowledge, the formation of fluorinated phosphines and their derivatives via direct addition is limited to a few reactions: the trifluoromethylfluorosulfonylation, the bromodifluoromethylation of allyldiphenyl phosphine oxide, the nucleophile mediated reaction of Ruppert–Prakash reagent (or perfluoroalkyltrimethylsilanes) with phosphites, or addition of LiC 2 F 5 to chlorinated phosphine and the unimolecular radical nucleophilic substitution reaction . Although the addition of an element‐hydrogen pair to an unsaturated C−C bond is a standard direct strategy to functionalize a molecular skeleton, hydro‐(hetero)element addition to allylic or propargylic phosphorus containing derivatives is rather limited .…”