C–H Fluoroalkylsulfinylation/Intramolecular Rearrangement for Precise Synthesis of Fluoroalkyl Sulfoxides

Abstract

An efficient methodology to access various fluoroalkyl sulfoxides bearing ortho/para-functionalized amine scaffolds from arylhydroxylamines is described. The transformation was featured with new electrophilic trifluoromethylthiolated reagents, good functional group tolerance, and late-stage modification of complex bioactive scaffolds, providing a rapid access to prepare numerous trifluoromethyl- and difluoromethyl-substituted sulfoxides. Mechanism studies and density functional theory calculations suggest this reaction goes through a nucleophilic trifluoromethylthiolation of arylhydroxylamine and subsequent internal 2,3-sigmatropic rearrangement involving a sulfur and oxygen transfer process.

Transition-Metal-Catalyzed Cross-Coupling of Chlorosilanes

“…Of note, almost at the same time, the Zhang group reported a similar C(sp 3 )–Si coupling reaction of vinylchlorosilanes under nickel catalysis. 28…”

Copper-catalyzed [1,3]-nitrogen rearrangement ofO-aryl ketoximesviaoxidative addition of N–O bond in inverse electron flow

“…2 The N–O bond cleavage, which is the driving force of the catalytic cycle, occurs via various mechanisms, including the oxidative addition to low-valent metal catalysts, homolytic cleavage, single electron transfer, and ionic cleavage, to generate unique reactive intermediates, such as aminyl radicals, 3 nitrenes, 4 and nitreniums. 5 In contrast to the catalytic transformations in which the oxygen atom of the N–O bond is typically cleaved off as a leaving group, rearrangement reactions yield molecules with both nitrogen and oxygen functional groups in an atom-efficient manner, 6,7 by using metal catalysts 8 and organocatalysts 9 under mild reaction conditions. However, [1,3]-nitrogen rearrangement reactions of O -arylhydroxylamine derivatives still remain unexplored to date although the fundamental rearrangement process can directly synthesize ortho -aminophenol derivatives 10,11 (Scheme 1).…”

Synthetic strategies for fluorosulfonylated compounds: application to click chemistry reactions

“…The association of sulfur and fluorine atoms has granted organic, biological and medicinal chemistry and materials sciences with most valuable groups, such as –SF 5 , 1–3 –SF 4 Cl, 1,2 –OSO 2 F, 4–6 –SO 2 CF 3 , 7–10 –S(O)CF 3 , 11,12 –SO 2 R F , –S(O)(N)(R)F, 13 and –SO 2 F, 14 among others.…”