Sulfones are key structural motifs in pharmaceuticals and agrochemicals, and their synthesis is of paramount importance in organic chemistry. While nucleophilic and electrophilic C(sp³)-sulfonylation are well documented, radical C(sp³)-sulfonylation remains elusive. Herein, we report the decarboxylative radical sulfonylation with sulfinates. With the merger of 4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene) and Cu(OTf)₂ as catalysts, the visible-light-induced reaction of redox-active esters of aliphatic carboxylic acids with organosulfinates at room temperature provides the corresponding decarboxylative sulfonylation products in satisfactory yields. This redox-neutral protocol exhibits broad substrate scope and wide functional group compatibility, enabling the late-stage modification of complex natural products and bioactive pharmaceuticals. The synthetic utility of the method is further demonstrated by the improved synthesis of anti-prostate cancer drug bicalutamide. A mechanism involving sulfonyl group transfer from Cu(II)–SO₂R to alkyl radicals is proposed.

砜是药物和农用化学品中的关键结构基序，其合成在有机化学中至关重要。虽然亲核和亲电的C（sp ³）-磺酰化已得到充分证明，但自由基C（sp ³）-磺酰化仍然难以捉摸。在本文中，我们报道了亚磺酸盐的脱羧自由基磺酰化。随着4CzIPN（1,2,3,5-四（咔唑-9-基）-4,6-二氰基苯）和Cu（OTf）₂的合并作为催化剂，脂肪族羧酸的氧化还原活性酯与有机亚磺酸盐在室温下的可见光诱导反应以令人满意的产率提供了相应的脱羧磺酰化产物。该氧化还原中性方案具有广泛的底物范围和广泛的官能团相容性，可以对复杂的天然产物和生物活性药物进行后期修饰。通过改进的抗前列腺癌药物比卡鲁胺的合成，进一步证明了该方法的实用性。提出了一种涉及磺酰基从Cu（II）-SO ₂ R转移至烷基的机理。