Visible-Light-Induced Trifluoromethylsulfonylation Reaction of Diazo Compounds Enabled by Manganese Catalysis

Abstract

A visible-light-induced trifluoromethylsulfonylation reaction of diazo compounds is herein reported. This developed synthetic method captures the relatively rare trifluoromethyl sulfone radicals via coordination to the Mn(acac) 3 catalyst, delivering the corresponding α-trifluoromethyl sulfone esters in good to moderate yields (up to 82%). This protocol exhibits broad substrate scope and is easily carried out under mild reaction conditions. Furthermore, a plausible mechanism of the reaction was investigated through DFT calculations.

Visible photons as ideal reagents for the activation of coloured organic compounds

“…Reduction to an anion followed by protonation enabled the attainment of the desired sulfonated products 96.2a-e, even on a gram scale. 319…”

Visible Light-Induced Reactions of Diazo Compounds and Their Precursors

“…In 2023, the groups of Guo, Song, and Xia reported a Mn-catalyzed trifluoromethylsulfonylation reaction of aryl diazoesters 57.1 to prepare α-trifluoromethyl sulfone esters 57.2 (Scheme ). This transformation features the generation of trifluoromethyl sulfone radicals A through coordination to the Mn­(acac) 3 catalyst, followed by their combination with a carbene, producing a stable radical intermediate B .…”

Mn(OAc)3-Promoted Sulfonation–ipso-Cyclization Cascade via the SO3– Radical: The Synthesis of Spirocyclic Sulfonates

“…Despite a few reported examples of sulfonated azaspiro­[4,5]-trienones and azaspiro­[4,5]-decanes in recent years, they are limited to sulfone preparation and are typically unable to undergo further modification. − In 2021, Wang’s group published the pioneering study on the sulfonation of electron-deficient alkenes using SO 3 – radicals for the synthesis of oxindole-based sulfonates . Recently, we have shown that the combination of Mn­(OAc) 3 − and K 2 S 2 O 5 − can effectively promote the oxidative sulfonation of functionalized alkenes via SO 3 – radicals as the key intermediate (Scheme A) . This success was attributed to the development of a suitable oxidative environment that matched well with the reactive SO 3 – radical.…”