Ni(II)-Catalyzed Sulfonylation of ortho C–H Bonds in Aromatic Amides Utilizing an N,N-Bidentate Directing Group

Abstract

The reaction of aromatic amides containing a 5-chloro-8-aminoquinoline moiety as the directing group with arylsulfonyl chlorides in the presence of Ni(OTf)2 as the catalyst results in sulfonylation at the ortho-position. Various arylsulfonyl chlorides can be used as the coupling partners.

A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

“…The amide derived from 5-chloro-8-aminoquinoline was employed as bidentate DG in the Ni( ii )-catalysed sulfonylation of carboxamides as reported by Chatani ( Scheme 85A ). 517 A mechanism involving a Ni( ii )/Ni( iv ) catalytic cycle was proposed, albeit the authors cannot rule out a radical pathway. Note that the 5-methoxy-8-quinolinyl derived amides led to the decomposition of the starting materials.…”

Nickel-catalyzed synthesis of diarylsulfides and sulfones via C–H bond functionalization of arylamides

“…During the course of the revision of the manuscript, a similar catalytic system was reported. 21 Initially, the reaction of 2-methyl-N-(quinolin-8-yl)benzamide (1a) with tosyl chloride (5a) was chosen as a model reaction and conducted under the optimized conditions of the sulfenylation reaction; however, the reaction did not take place. We thus optimized the reaction conditions and the results are shown in Table 4.…”

Nickel‐Catalyzed Benzylation of C−H Bonds in Aromatic Amides with Benzyltrimethylammonium Halides

“…On the basis of these results, we postulated that the benzylation of C−H bonds aromatic amides could be achieved with benzylammonium salt being used in place of PhMe 3 N + I − . To verify this hypothesis, the reaction of an aromatic amide bearing a 5‐chloro‐8‐aminoquinoline moiety as a directing group,, 1a and 2 equivalents of BnMe 3 N + Br − was examined in the presence of Ni(OTf) 2 (10 mol %) and Na 2 CO 3 (2 equiv) in toluene at 140 °C, with a reaction time of 20 h (Scheme ). As a result, the ortho‐benzylation product 2a was produced in 99 % isolated yield.…”