New organosulfur-based strategies for efficient and selective organic synthesis.

有机硫化合物在促进人类健康和福祉方面发挥着重要作用。四分之一的最 处方药含有硫，硫是所有批准药物中除氧之外最常见的杂原子 和氮。含硫官能团还使得能够进行各种反应，所述反应用于 合成天然产物、生物探针、治疗剂、染料和高级功能材料。 然而，有机硫化合物的多样性和多能性反应性导致低的化学-、区域-和 立体选择性对有机化学中立体选择性和区域选择性方法的发展产生不利影响 合成.这项研究的长期目标是通过精简来推进有机合成领域 合成重要的有机硫化合物，并系统地开发其区域和 立体选择性转化为广泛类别的有价值的官能团和结构基序。的 中间氧化态有机硫试剂亚磺酸盐具有解决目前限制的潜力， 有机硫化合物的合成方法以及能够进行新的区域选择性和立体选择性反应， 广泛的官能化小分子。然而，缺乏有效的合成方法， 亚磺酸盐直接从丰富的前体和差距的基本认识，几乎完全 亚磺酸酯在立体选择性C = C键形成交叉偶联反应中的未探索的反应性 本研究的总体目标是开发由丰富的前体合成亚磺酸酯的方法 并开发亚磺酸酯的区域和立体选择性C-C键形成反应。这一目标将是 通过系统地开发三个研究课题，包括目前难以捉摸的合成 方法.在第一部分中，将研究中间体亚磺酸酯的立体分散催化交叉偶联反应， 发展成为一个广泛的合成平台，以获得高和可预测的共轭二烯和多烯 区域和立体选择性。在第二部分，一个通用的平台，利用丰富的C-H键的手段， 将开发区域选择性C-H亚磺化。第三部分是烯烃的催化亚磺化反应 从烯烃的丰度和反应性中提取的反应。在完成这项研究计划后，广泛的 一系列目前具有合成挑战性的官能化分子，包括含硫分子， 有机合成和药物发现应用变得容易获得，有助于改善 通过更有效地合成小分子生物探针和治疗药物， 剂.

Organosulfur compounds have a major role in advancing human health and well-being. A quarter of the most prescribed drugs contain sulfur, and sulfur is the most common heteroatom in all approved drugs after oxygen and nitrogen. The sulfur-containing functional groups also enable a variety of reactions that are used to synthesize natural products, biological probes, therapeutic agents, dyes, and advanced functional materials. However, the diverse and pluripotent reactivities of organosulfur compounds lead to low chemo-, regio- and stereoselectivities that adversely affect development of stereo- and regioselective approaches in organic synthesis. The long-term goal of this research is to advance the field of organic synthesis by streamlining synthetic access to centrally important organosulfur compounds and systematically developing their regio- and stereoselective transformations to broad classes of valuable functionalities and structural motifs. The intermediate oxidation state organosulfur reagents sulfinates have the potential to solve limitations of current methods of synthesis of organosulfur compounds and to enable new regio- and stereoselective reactions to a wide range of functionalized small molecules. However, there is a lack of efficient methods of synthesis of sulfinates directly from abundant precursors and a gap in fundamental understanding of the nearly entirely unexplored reactivity of sulfinates in the context of stereoselective C‒C bond forming cross-coupling reactions The overall objective of this research is to develop methods of synthesis of sulfinates from abundant precursors and to develop regio- and stereoselective C−C bond forming reactions of sulfinates. This objective will be accomplished by systematically developing three research topics encompassing currently elusive synthetic methods. In the first part, stereodivergent catalytic cross-coupling reactions of intermediate sulfinates will be developed into a broad synthetic platform to access conjugated dienes and polyenes with high and predictable regio-and stereoselectivity. In the second part, a generic platform for harnessing abundant C−H bonds by means of a regioselective C−H sulfination will be developed. The third part is focused on catalytic alkene sulfination reactions to draw from abundance and reactivity of alkenes. Upon completion of this research program, a broad range of currently synthetically challenging functionalized molecules including sulfur-containing ones will become readily accessible for organic synthesis and drug discovery applications, contributing to improvement of human healthcare through more efficient syntheses of small molecule biological probes and therapeutic agents.