Hetaryl Bromides Bearing the SO₂F Group – Versatile Substrates for Palladium‐Catalyzed C–C Coupling Reactions

Abstract

Synthesis of novel five‐ and six‐membered heteroaromatic sulfonyl fluorides bearing bromine atom at various positions of the heterocyclic ring is described. The synthetic utility of these compounds is demonstrated by the Suzuki, Stille, and Negishi cross‐coupling reactions, which proceeded chemoselectively at the aryl bromide moiety with 69–98 % yields. The tolerance of the SO2F group towards the coupling reaction conditions was confirmed in most of the experiments. The proposed method was efficient for either sp2–sp2 or sp2–sp3 C–C couplings. The developed procedure provides rapid access to various substituted heterocyclic sulfonyl fluorides.

The Emerging Applications of Sulfur(VI) Fluorides in Catalysis

“…In 2018, Grygorenko and co-workers reported a Pd-catalyzed Suzuki ( Scheme 17 ), Stille, and Negishi cross-coupling reactions for the synthesis of heteroaromatic sulfonyl ( 84 ) using the corresponding organometallic reagents with bromoheteroaromatic sulfonyl fluorides ( 83 ). 60 In the majority of cases, the SO 2 F group is stable to the reaction conditions and does not compete with the aryl bromide coupling.…”

“…toward C–C, C–N, C–O, and other bond formations. 60 Contributions to this idea will be transformational in expanding their synthetic utility. Lastly, we are just scratching the surface in the exploration of single-electron transformations using S(VI) fluorides.…”

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

“…metal-catalyzed cross-coupling reactions, namely, Ullmann, [247,248] Stille, [249][250][251][252] Sonogashira, [214,253] Heck, [197,[254][255][256] SuzukiÀ Miyaura [257][258][259] reactions, BuchwaldÀ Hartwig amination, [260,261] borylation, [214,262] etc. ; ii.…”

Synthesis of Fused Pyridine Carboxylates by Reaction of β-Alkoxyvinyl Glyoxylates with Amino Heterocycles

“…17,[40][41][42][43] To the best of our knowledge, synthetic utility of alkoxyvinyl glyoxylates for the construction of fused pyridines was not demonstrated to date. In continuation of our work in the field of pyridine chemistry, [44][45][46][47][48][49][50] we have now aimed at the study of the low-molecular-weight alkoxyvinyl glyoxylates 11a-c as CCC bis-electrophiles in the reactions with common NCC binucleophiles 9 (Scheme 1).…”