Exploiting Chalcogen-Containing Compounds in Donor-Acceptor Cyclopropane and Cyclobutane Chemistry: Access to Four- to Nine-Membered Heterocycles

在供体-受体环丙烷和环丁烷化学中开发含硫化合物：获得四至九元杂环

• 批准号: 457026728
• 负责人: Professor Dr. Daniel B. Werz
• 金额: --
• 依托单位: Institut für Organische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/457026728?language=en
• 关键词: Exploiting; Chalcogen; Containing; Compounds; Donor

In this project, reactions of donor-acceptor cyclopropanes and cyclobutanes with chalcogen-containing compounds will be investigated. Previous work by the group has shown that their high nucleophilicity is ideally suited to initiate ring opening and cycloaddition reactions of these polarized three-membered rings.In the first sub-project, donor-acceptor cyclopropanes are to be expanded into the corresponding four-membered rings under Lewis acid catalysis by inserting a chalcogen atom (S or Se). Reagents that not only contain a nucleophilic chalcogen but also carry a corresponding leaving group on the chalcogen (e.g. thiosulfonates, RSeSeLi etc.) are to serve as chalcogen carriers. A slightly modified reaction design should also allow the insertion of two chalcogens, be they the same or different, into the corresponding five-membered rings with endo-dichalcogenide subunits. Similar reactions should be carried out on the slightly less strained donor-acceptor cyclobutanes in order to arrive at analogous five- and six-membered rings containing chalcogens. With the aid of chiral ligands that complex the Lewis acid, some of these transformations should also be carried out with a dynamic kinetic resolution.The second subproject is devoted to (3+4) -, (3+5) - and (3+6)-cycloadditions of donor-acceptor cyclopropanes with four, five and six atomic components to build seven-, eight- and nine-membered ring systems. In order to obtain sulfur-containing seven-membered rings, benzothietes as a 4-atom component are to be reacted with the polarized three-membered rings under Lewis acid catalysis. The synthesis of eight-membered rings based on the cyclopropanes is to be carried out by means of synergistic catalysis. Vinyl-substituted epoxides, thiiranes and also aziridines as 5-atom components are to be activated by means of Pd catalysis and reacted with the three-membered rings activated by a Lewis acid. Similar reactions starting from vinyl-substituted oxetanes, thietanes and azetidines as 6 atom components should allow access to nine-membered ring systems. The enantioselectivity of the reactions could be controlled by means of chiral ligands on the Lewis acid as well as on the Pd to give a matched or mismatched case.

在这个项目中，将研究供应者环丙烷和环形植物与含chalcogen的化合物的反应。该小组的先前工作表明，它们的高亲核性非常适合启动这些极化三元的环的打开环和环载反应。在第一个子项目中，供体检测器环露植物将扩展到相应的四元环中，通过插入chalccogen（s or sepogen）（s or sepogen）（s or Sepogen）（S or Sepogen）（s or Sepogen）。不仅含有亲核性沙尔氏菌的试剂，而且还携带相应的离开基因（例如硫代硫酸盐，rseseli等），是作为chalcogen载体。稍微修改的反应设计还应允许将两个墨西哥蛋白酶（无论是相同还是不同）插入带有内甲基甲基元素亚基的相应五元环中。为了获得含有沙尔卡胶的类似的五元和六元环，应对稍微不紧张的供体循环机构进行类似的反应。借助刘易斯酸复合的手性配体，其中一些转化也应采用动态动态分辨率进行。第二个子项目专用于（3+4） - （（3+5） - （3+5） - 和（3+6） - 供体accceptor cyceptor cyclopanes与四，五和五个环的组成 - 六个环上的组成 - 五个环境，以及八个环的组成 - 六个 - 五个环。为了获得含硫的七元环，苯佐比作为4原子成分应与刘易斯酸催化下的极化三元环反应。基于环丙烷的八元环的合成应通过协同催化进行。乙烯基取代的环氧化物，硫烷和氮杂胺作为5个原子分量应通过PD催化激活，并与刘易斯酸激活的三元环反应。从乙烯基取代的Oxetanes，thietanes和Azetidines开始的类似反应与6个原子成分应允许进入9元环系统。反应的对映选择性可以通过刘易斯酸以及PD上的手性配体来控制，以产生匹配或不匹配的情况。