单取代磺酰肼的碳-硫键生成反应

Monosubstituted sulfonyl hydrazides have been widely used in organic synthesis, which focuses on the transformations of the hydrazine unit and hardly involves the sulfonyl unit in the formation of new target bonds. We plan to develop new reactions, methods, and applications for the formation of C-S bonds by using monosubstituted sulfonyl hydrazides as sulfonylating or sulfenylating agents under certain conditions. The asymmetric dehydrazinative alkylation of monosubstituted sulfonyl hydrazides with racemic allylic amines, alcohols, ethers, esters, or chiral primary ferrocenylmethylamines has been proposed for the synthesis of chiral sulfones with high optical purities and for the attainment of highly efficient kinetic resolution of racemic allylic amines, alcohols, ethers, and esters. We plan to develop C-S bond-forming reactions between monosubstituted sulfonyl hydrazides and nucleophiles such as aromatic compounds, active methylene compounds, boronic acids, and organosilicons for the synthesis of unsymmetrical thioethers. Moreover, various cyclization reactions of monosubstituted sulfonyl hydrazides with alkynes, alkenes, N-allylhydrazines or hydroxylamines have been proposed for the synthesis of sulfur- and/or nitrogen-containing heterocycles. These proposed C-S bond-forming reactions not only provide facile access to several types of important organic compounds, but also are featured by employing readily accessible and odorless starting materials, tolerating water and air, involving simple operation, and being friendly to the environment.

单取代磺酰肼虽然被广泛应用于有机合成中，但仅集中于其肼基结构单元的利用，而目标化学键的生成几乎不涉及磺酰基结构单元的改变。我们拟在特定条件下用单取代磺酰肼充当砜化试剂或者硫醚化试剂，发展生成碳-硫键的新反应、新方法和新应用。拟发展单取代磺酰肼与外消旋烯丙型胺、醇、醚、酯及手性一级二茂铁基甲基胺的不对称去肼基烷基化反应，合成高光学纯度的手性砜，实现外消旋烯丙型胺、醇、醚、酯的高效动力学拆分。拟发展单取代磺酰肼与芳香化合物、活泼亚甲基化合物、有机硼酸、有机硅等亲核试剂的碳-硫键生成反应，合成非对称硫醚。拟发展单取代磺酰肼与炔烃、烯烃、N-烯丙基肼或者羟胺的成环反应，构建含硫、氮的杂环。这些拟发展的碳-硫键生成反应不仅可以合成多种类型的重要有机化合物，而且具有原料易得、无恶臭气味、容忍水和空气、操作简便、对环境友好等优点。

我们在前期研究中成功地将磺酰肼开发成一种新型硫醚化试剂，在此基础上发展了磺酰肼与N-芳基丙烯酰胺、碘代环烯烃、有机硼酸、吲哚等有机物的硫醚化反应，合成了结构多样的硫醚和杂环化合物。相对于传统硫醚化反应而言，这些新反应具有原料易得、无恶臭气味、容忍水和空气、操作简便、对环境友好等优点。在此期间，磺酰肼的硫醚化反应受到化学家的广泛关注，国内外有多个研究组开展了相关研究工作。我们以磺酰肼作为砜化试剂，发展了钯催化的磺酰肼与烯丙醇的去肼基烯丙化反应，进一步发展了磺酰肼和钯络合物共同催化的烯丙化反应，实现了外消旋烯丙醇、烯丙胺的动力学拆分，具有对映选择性高、试剂便宜、操作简便等优点。我们发展了磺酰肼及其类似物的氧化去肼化反应，成功地将TfNHNHBoc开发成一种新型三氟甲基化试剂，将N-羟基磺酰胺开发成一种新型硫醚化试剂，将肼基甲酰胺开发成一种新型氨基甲酰化试剂。此外，我们还发展了一些有机胺和亚胺的碳-氮键断裂反应。在Org. Lett.、Chem. Commun.、Chem. Eur. J.、J. Org. Chem.、Adv. Synth. Catal.等重要学术刊物上发表论文17篇，多篇论文被Synfacts、X-MOL网站和Organic Chemistry Portal网站等积极评论。