Aromatic and Benzylic C–H Bond Functionalization Upon Reaction between Nitriles and Perfluoroalkyl Sulfoxides

Abstract

We studied the thermal behavior of some intermediates formed by reaction of nitriles with perfluoroalkyl sulfoxides upon trifluoromethanesulfonic anhydride activation. Bistriflate ketal 3, precursor of sulfilimine 1, may undergo a rearrangement to sulfanyl nitrile 5 after triflic acid elimination under thermal conditions. With p-tolyl trifluoromethyl sulfox-

Divergent Preparation of Fluoroalkylated Sulfilimine and Sulfilimino Iminium Salts

“…We disclosed a Ritter-like reaction, between nitriles and sulfoxides activated by trifluoromethanesulfonic anhydride, giving rise to a wide . [5] In the same work, we also described the facile synthesis of perfluorinated sulfoximines either by oxidation of pure sulfilimines 4 or directly in a one-pot process from sulfoxides.…”

Perfluoroalkylated Bis(sulfilimine)s and Bis(sulfoximine)s by a Ritter‐Type Reaction

“…Our divergent synthetic pathway started with simple perfluoroalkyl sulfoxides i. [15] The formation of these sulfur(II) compounds (i.e., vi) can been explained by a transposition process. [11] Structure ii rapidly appeared as a common platform and key intermediate to routes that provide molecular diversity.…”

“…A Ritter-like reaction with nitriles as nucleophiles afforded bis(trifluoromethanesulfonate) ketal ii. [11] Structure ii rapidly appeared as a common platform and key intermediate to routes that provide molecular diversity. Its hydroly-sis afforded acylsulfilimines iii, which were either isolated or smoothly oxidized by potassium permanganate to give the corresponding sulfoximines iv (see Scheme 1, route a).…”

“…[14] Heating intermediate ii before hydrolysis led to the divergent synthetic pathway that allowed for the isolation of perfluoroalkyl thioethers vi as the major product (see Scheme 1,route b). [15] The formation of these sulfur(II) compounds (i.e., vi) can been explained by a transposition process. We assume that the pathway started with the elimination of trifluoromethanesulfonic acid to form intermediate vii, which could undergo a pericyclic reaction.…”

The emergence of sulfoxide and iodonio-based redox arylation as a synthetic tool

“…From a synthetic point of view, a particularly attractive prospect is the identification of coupling partners beyond those showed in Figure 1. As already discussed, known examples include the engagement of amides and ynamides developed by Maulide et al 19 Also noteworthy is the possibility of engaging simple aliphatic nitriles as coupling partners, demonstrated in 2009 by Magnier et al 31 The method relied on a Claisen-type rearrangement of fluoroalkyl acylsulfilimines obtained via a Ritter-type activation of nitriles (Scheme 32). Although only MeCN and n-PrCN were coupled in meaningful yields, this work nevertheless serves as a proof of concept.…”