近日，台州学院吴劼团队报道了负载环烷醇与亚硫酸盐的光催化开环亚砜化反应。该研究于2026年5月27日发表在《中国化学》杂志上。

亚砜结构广泛存在于天然产物和生物活性分子中，同时也是有机硫化合物制备的关键中间体，以及过渡金属催化转化中的配体或导向基团。因此，亚砜的合成一直是长期的研究热点。过去五年中，利用易得的亚磺酸盐进行亚磺酰化反应，已成为向分子中引入亚磺酰基团的一种颇具前景的策略。在此背景下，烷基醇常被用作亲核试剂，与亚磺酸盐和酰化试剂反应，从而合成亚磺酸酯及其手性变体。然而，烷基醇在亚磺酰化反应中直接作为自由基前体的潜力尚未被探索。

研究组首次报道了光催化下张力环烷醇的开环亚磺酰化反应，为合成带有远程羰基的亚砜提供了一条直接途径，传统上这类化合物需要通过连续的硫醚合成和单氧化步骤获得。在该方法中，使用适当的酰化试剂时，芳基亚磺酸盐和烷基亚磺酸盐均能作为有效的底物。机理上，有机光催化促进了环丙醇和环丁醇生成烷氧自由基。这些烷氧自由基的高环张力驱动了快速的β-断裂过程，生成瞬态的烷基自由基。

随后，该自由基与原位生成的亚磺酰基砜（由亚磺酸盐和酰化试剂反应产生）发生自由基取代反应，得到γ-和δ-酮基亚砜。这种一锅法具有反应条件温和、亚磺酰基来源易得以及化学选择性良好的特点。产物中的羰基和亚磺酰基单元可进一步衍生化，一系列成熟的转化反应证明了这一点。

附：英文原文

Title: Photocatalytic Ring-Opening Sulfinylation of Strained Cycloalkanols with Sulfinates

Author: Yun Zhang, Wenquan Liao, Zhehao Zhang, Yong-Ke He, Jun Zhang, Jie Wu

Issue&Volume: 2026-05-27

Abstract: Sulfoxides are structural motifs widely found in natural products and bioactive molecules, while also serving as linchpins for organosulfur compound preparation and as ligands or directing groups for transition-metal-catalyzed transformations. This makes their synthesis a long-standing focus of research. Over the past five years, sulfinylation using readily available sulfinates has proven to be a promising strategy for introducing sulfinyl groups into molecules. In this context, alkyl alcohols have been commonly employed as nucleophiles to react with sulfinates and acylating reagents, enabling the synthesis of sulfinate esters and their chiral variants. However, the potential of alkyl alcohols to act directly as radical precursors in sulfinylation remains unexplored. Herein, we report the first photocatalytic ring-opening sulfinylation of strained cycloalkanols, offering a direct route to sulfoxides with a remote carbonyl group that were traditionally accessed via sequential thioether synthesis and mono-oxidation. In this protocol, with an appropriate acylating reagent, both aryl and alkyl sulfinates are competent substrates. Mechanistically, organic photocatalysis promotes the generation of alkoxy radicals from cyclopropanols and cyclobutanols. The high ring strain of these alkoxy radicals drives a fast β-scission process, furnishing transient alkyl radicals. Subsequent radical substitution with in situ generated sulfinyl sulfones (from sulfinates and acylating reagent) delivers γ- and δ-keto sulfoxides. This one-pot method is characterized by mild reaction conditions, readily available sulfinyl sources and good chemoselectivity. The carbonyl and sulfinyl moieties in the products proved amenable to further derivatization, as shown by a series of well-established transformations.

DOI: 10.1002/cjoc.70631

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70631