Harnessing Sulfur Dioxide for Catalysis

利用二氧化硫进行催化

• 批准号: EP/K00803X/1
• 负责人: Michael Willis
• 金额: $ 45.28万
• 依托单位: University of Oxford
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2013
• 资助国家: 英国
• 起止时间: 2013 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FK00803X%2F1
• 关键词: Harnessing; Sulfur; Dioxide; Catalysis

Sulfonyl units, that is the -SO2- arrangement of atoms, are functional groups that feature in a significant number of pharmaceuticals, argochemcials and materials. Conventional syntheses of these types of molecules usually involve two or three synthetic operations, and often feature low-yielding steps. The chemistry involved also limits the substrates that can be converted to sulfonyl-containing molecules. This proposal seeks to develop an alternative synthesis of this class of molecules; the proposed synthesis will be achieved in a single operation, employ readily available reagents and substrates, and be conducted under mild conditions. The key to the proposed synthesis is to employ a three-component synthesis involving the catalytic combination of an aryl halide, an nucleophile and sulfur dioxide. Achieving the synthesis in a single operation will have significant advantages in terms of waste production, energy required, as well as the time needed to prepare the desired compounds. These are important considerations for both small scale discovery synthesis, as well as the large scale synthesis of these materials. The developed methodology should also be applicable to the preparation of related molecules derived from alternative starting materials such as non-functionalised arenes or alkene and alkynes. The project will explore the application of the developed method to the synthesis or selected target structures that are difficult to access using conventional methods, and to the synthesis of heterocycles. Application of the developed catalytic methods to the synthesis of new materials, using polymerisation chemistry, will also be preliminarily investigated.

磺酰基单元，即原子的-SO2-排列，是在大量药物、药物化学品和材料中具有特征的官能团。这些类型的分子的常规合成通常涉及两个或三个合成操作，并且通常具有低产率步骤。所涉及的化学也限制了可以转化为含磺酰基分子的底物。该提案旨在开发这类分子的替代合成;所提出的合成将在单一操作中实现，采用容易获得的试剂和底物，并在温和条件下进行。提出的合成的关键是采用一个三组分的合成涉及的芳基卤化物，亲核试剂和二氧化硫的催化组合。在单一操作中实现合成将在废物产生、所需能量以及制备所需化合物所需时间方面具有显著优势。这些对于这些材料的小规模发现合成以及大规模合成都是重要的考虑因素。所开发的方法学还应适用于制备衍生自替代起始材料（如非官能化芳烃或烯烃和炔烃）的相关分子。该项目将探索将开发的方法应用于合成或选择使用常规方法难以获得的目标结构，以及杂环的合成。还将初步研究开发的催化方法在使用聚合化学合成新材料中的应用。

项目成果

One-pot palladium-catalyzed synthesis of sulfonyl fluorides from aryl bromides.

• DOI: 10.1039/c6sc03924c
• 发表时间: 2017-02-01
• 期刊: Chemical science
• 影响因子: 8.4
• 作者: Davies AT;Curto JM;Bagley SW;Willis MC
• 通讯作者: Willis MC

Combining organometallic reagents, the sulfur dioxide surrogate DABSO, and amines: a one-pot preparation of sulfonamides, amenable to array synthesis.

• DOI: 10.1002/anie.201409283
• 发表时间: 2015-01-19
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Deeming, Alex S.;Russell, Claire J.;Willis, Michael C.
• 通讯作者: Willis, Michael C.

One-Pot Sulfonamide Synthesis Exploiting the Palladium-Catalyzed Sulfination of Aryl Iodides

• DOI: 10.1055/s-0035-1560578
• 发表时间: 2016-01-01
• 期刊: SYNLETT
• 影响因子: 2
• 作者: Flegeau, Emmanuel Ferrer;Harrison, Jack M.;Willis, Michael C.
• 通讯作者: Willis, Michael C.

Palladium-catalyzed synthesis of ammonium sulfinates from aryl halides and a sulfur dioxide surrogate: a gas- and reductant-free process.

• DOI: 10.1002/anie.201404527
• 发表时间: 2014-09-15
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Emmett, Edward J.;Hayter, Barry R.;Willis, Michael C.
• 通讯作者: Willis, Michael C.

Palladium(II)-Catalyzed Synthesis of Sulfinates from Boronic Acids and DABSO: A Redox-Neutral, Phosphine-Free Transformation.

• DOI: 10.1002/anie.201508370
• 发表时间: 2016-01-11
• 期刊: Angewandte Chemie (International ed. in English)
• 作者: Deeming AS;Russell CJ;Willis MC
• 通讯作者: Willis MC