Anti-Markovnikov hydrosulfenylation of unactivated alkenes/alkynes via visible-light organic photocatalysis†

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry Pub Date : 2025-05-22 DOI:10.1039/d5gc02604k

Jiayi Gu , Meixiu Xin , Zhuo Cheng , Zhiru Zou , Zhibo Du , Xinyi Cheng , Yan Wang , Yong Zou

{"title":"Anti-Markovnikov hydrosulfenylation of unactivated alkenes/alkynes via visible-light organic photocatalysis†","authors":"Jiayi Gu , Meixiu Xin , Zhuo Cheng , Zhiru Zou , Zhibo Du , Xinyi Cheng , Yan Wang , Yong Zou","doi":"10.1039/d5gc02604k","DOIUrl":null,"url":null,"abstract":"<div><div>Photocatalytic difunctionalization of alkenes/alkynes offers one of the most efficient methods to access structurally diverse molecules from readily available precursors with excellent atom- and step-economic attributes. However, reactions involving unactivated alkenes/alkynes have been proven to be elusive and remain underdeveloped. Here, we report a Rose Bengal (RB)-catalyzed hydrosulfenylation of unactivated alkenes/alkynes using thiols as abundant starting materials and citric acid as a biomass-derived acid additive. Mechanistic studies revealed that the transformation proceeds <em>via</em> thiol–ene/yne click reactions, followed by reactive oxygen species and <em>in situ</em>-generated peroxide-mediated oxidation processes. This protocol exhibits good functional group compatibility with excellent regioselectivity, affording a diverse range of aryl alkyl, dialkyl, and vinyl sulfoxides as valuable synthetic building blocks in organic synthesis.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 26","pages":"Pages 7763-7770"},"PeriodicalIF":9.2000,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Green Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S1463926225004844","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

Abstract

Photocatalytic difunctionalization of alkenes/alkynes offers one of the most efficient methods to access structurally diverse molecules from readily available precursors with excellent atom- and step-economic attributes. However, reactions involving unactivated alkenes/alkynes have been proven to be elusive and remain underdeveloped. Here, we report a Rose Bengal (RB)-catalyzed hydrosulfenylation of unactivated alkenes/alkynes using thiols as abundant starting materials and citric acid as a biomass-derived acid additive. Mechanistic studies revealed that the transformation proceeds via thiol–ene/yne click reactions, followed by reactive oxygen species and in situ-generated peroxide-mediated oxidation processes. This protocol exhibits good functional group compatibility with excellent regioselectivity, affording a diverse range of aryl alkyl, dialkyl, and vinyl sulfoxides as valuable synthetic building blocks in organic synthesis.

Abstract Image

查看原文本刊更多论文

可见光有机光催化下非活化烯烃/炔烃的反马尔可夫尼科夫氢亚砜化研究

光催化双官能化烯烃/炔提供了一种最有效的方法，从易于获得的具有优异原子经济和阶梯经济属性的前驱体中获得结构多样的分子。然而，涉及非活化烯烃/炔的反应已被证明是难以捉摸的，仍然不发达。在这里，我们报道了玫瑰孟加拉（RB）催化的未活化的烯烃/炔的氢亚砜化反应，使用硫醇作为丰富的起始材料，柠檬酸作为生物质衍生的酸添加剂。机理研究表明，转化过程通过巯基/炔键反应进行，然后是活性氧和原位生成的过氧化物介导氧化过程。该方案具有良好的官能团相容性和优异的区域选择性，提供了各种各样的芳烷基、二烷基和乙烯基亚砜作为有机合成中有价值的合成基石。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Green Chemistry 化学-化学综合

CiteScore

16.10

自引率

7.10%

发文量

677

审稿时长

1.4 months

期刊介绍： Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.