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。最多的四分之一 处方药中含有硫，在所有批准的药物中，硫是除氧气之外最常见的杂原子 和氮气。含硫官能团还能进行各种反应，用于 合成天然产物、生物探针、治疗剂、染料和先进功能材料。 然而，有机硫化合物的多样性和多效性导致了较低的化学、区域和 对有机立体和区域选择性方法的发展产生不利影响的立体选择性 综合。这项研究的长期目标是通过简化来推动有机合成领域的发展 综合获取中心重要的有机硫化合物，并系统地开发其区域和 向有价值的功能和结构主题的广泛类别的立体选择性转换。这个 中间氧化态有机硫试剂亚硫酸盐有可能解决电流的局限性 有机硫化合物的合成方法以及使新的区域和立体选择性反应成为可能 广泛的官能化小分子。然而，目前还缺乏有效的合成方法。 直接从丰富的前体和对亚硫酸盐的基本认识的差距，几乎完全 亚硫酸盐在立体选择性C-C键形成交叉偶联反应中的未知反应性 这项研究的总体目标是开发从丰富的前体合成亚硫酸盐的方法。 以及开发亚硫酸盐的区域和立体选择性C-−-C成键反应。这一目标将是 通过系统地开发三个研究主题来完成，包括目前难以捉摸的 方法：研究方法。在第一部分中，我们将讨论中间体亚硫酸盐的立体发散催化交叉偶联反应 发展成为获得高含量和可预测的共轭双烯和多烯的广泛合成平台 区域和立体选择性。在第二部分中，建立了一个利用丰富的C-−氢键的通用平台 将开发一种区域选择性的C−H亚硫化。第三部分重点研究了催化烯烃亚硫化反应。 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，一个广泛的 包括含硫分子在内的一系列目前具有合成挑战性的官能化分子将 使有机合成和药物研发应用变得易于访问，有助于改进 通过更有效地合成小分子生物探针和治疗性药物 探员们。

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.