基于硫三负自由基(S3•−)或廉价过渡金属催化下C-S键构建反应实现功能性含硫化合物精准合成及其应用研究

Organic sulfur compounds are second only to oxygen or nitrogen containing organic compounds, which are widely found in nature and organism and widely used in pesticide, medicine and materials. Therefore, it is of great theoretical and practical significance to develop new sulfur containing reagents, explore new synthetic methods for the construction of C-S bonds, and study the synthesis of novel sulfur containing functional molecules, sulfur containing natural products and their analogues..Based on our previous research work on the construction of the C-S bonds, we intend to carry out research on efficient construction C-S bonds following two aspects, creatively solve the problems of C-S construction faces:.(1) In this project, we are going to study the generation of tri-sulfur radical anion (S3•−) and electrons from the mixture of K2S in DMF. We will further study the reaction of electron catalysis reaction and the reaction involving tri-sulfur radical anion (S3•−) under transition-metal-free conditions. .a) Electron-catalyzed reductive reactions..b) The reaction of tri-sulfur radical anion (S3•−) with different radical acceptors and their applications..c) S insertion reaction based on tri-sulfur radical anion (S3•−). and their applications...(2) We will focus on the efficient C-S formation reactions based on electrophilic sulfur reagents catalyzed by inexpensive transition metal or under transition-metal free conditions. .(a) Study on the design and synthesis of novel electrophilic sulfur reagents and their applications in the efficient construction of C-S bond under transition-metal free conditions..(b) Study on the efficient synthesis of sulfide compounds and their derivatives from halogenated compounds and electrophilic sulfur reagents catalyzed by inexpensive transition metal..(c) Design, synthesis and application of other functional sulfur containing reagents.. .Through the implementation of this project, we are able to solve some important scientific problems in the construction of C-S bonds:.(a) This study will promote the research on the new sulfur-centered radicals especially the application of S3•− in organic synthesis, which will provide an innovative way to implement C-S construction under transition-metal free conditions. .(b) This study will the innovative design and synthesis of novel electrophilic sulfur reagents. We will study the C-S formation reactions utilizing electrophilic sulfur catalyzed by inexpensive transition metal or under transition-metal free conditions. This study will innovative develop of new generic strategies for the precision synthesis of sulfides especially the alkyl sulfides..(c) Efficient synthesis of functional sulfur-containing ligands and natural products based on the new developed C-S bond construction strategies. .The research and improvement of the project will have a long-term practical significance for the efficient construction of sulfur containing organic molecules based on C-S bonds formations.

(1)研究基于硫三负自由基(S3•−)C-S键构建实现有机硫化合物精准合成及其应用。(2)研究廉价过渡金属催化或无过渡金属催化剂条件下基于亲电性含硫试剂高效构建C-S反应。通过本项目的实施，我们能够解决C-S键构建化学研究面临的一些重要科学问题：(a)推动含新硫自由基特别是S3•−在有机合成中的应用研究，创新性地实现C-S键构建新化学研究;对无过渡金属条件下新插硫反应以及电子催化有机反应机理以及应用进行深入研究。(b)创新性地设计、合成新型亲电性硫试剂，研究廉价过渡金属催化或无过渡金属催化剂条件下基于亲电性含硫试剂高效构建C-S反应，创新性地发展新的、通用策略实现硫醚特别是烷基硫醚化合物的精准合成。(c)利用新发展的C-S键构建方法学，实现功能性含硫配体、天然产物的高效合成。该项目的研究与完善，对基于C-S键高效构建含硫功能有机分子将具有长远的理论和现实意义。

通过本项目的实施，我们能够解决C-S键构建化学研究面临的一些重要科学问题：(a)推动了含新硫自由基特别是S3•−在有机合成中的应用研究，创新性地实现C-S键构建新化学研究;对无过渡金属条件下新插硫反应以及电子催化有机反应机理以及应用进行深入研究。(b)创新性地设计、合成新型亲电性硫试剂，研究廉价过渡金属催化或无过渡金属催化剂条件下基于亲电性含硫试剂高效构建C-S反应，创新性地发展新的、通用策略实现硫醚特别是烷基硫醚化合物的精准合成。(c)基于异腈发展了一系列C-S、C-Se键构建反应。(d)发展了一系列异腈参与的新反应。