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Development of carbon-carbon bond-forming reactions via novel sulfur-containing reactive species

通过新型含硫活性物质开发碳-碳键形成反应

基本信息

批准号：
15550088
负责人：
MURAI Toshiaki
金额：
$ 2.37万
依托单位：
Gifu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

It is one of the most important problems in synthetic organic chemistry to develop and discover new highly selective and efficient synthetic reactions. Functionalities such as carbonyl, alkenyl, and alkynyl groups have been widely utilized to develop new transformations of carbon-skeletons. On the other hand, the focus was laid on sulfur isologues of amides, i.e., thioamides. The generation of reactive species from thioamides and their application to carbon-carbon bondforming reactions were explored.・Carbon-carbon bond-forming reactions via sulfur-containing anionic speciesThe reaction of thioamides with two equivalents of BuLi proceeded smoothly at ℃ -rt to generate thioamide dianions. The ring opening of oxiranes with the thioamide dianions took place selectively at the carbon atom adjacent to the nitrogen atom of the dianions, followed by the hydrolytic workup to regenerate thiocarbonyl groups. This reaction was applied to a variety of oxiranes, and synthetic methods for 1,3-amino alcohols and oxazines, which are one of the most useful compounds, were provided.・Carbon-carbon bond-forming reactions via sulfur-containing cationic speciesMethylation of thioamides with MeOTf was complete within a few seconds to give thioiminium salts. Then, the addition of lithium acetylides and organomagnesium reagents to the obtained thioiminium salts was carried out. As a result, tertiary progaryl amines bearing new carbon skeletons were obtained with high efficiency and selectivity. Additionally, the addition of organozinc acetylides to the thioiminium salts leading to tertiary amines with enyne skeletons was also achieved.In summary, the species used in the studies are derived from the thioamides, which are readily prepared from commercially available materials. On the basis of the species new synthetic routes to valuable derivatives, which were not easy to be obtained by known methods, were established.

开发和发现新的高选择性、高效的合成反应是合成有机化学的重要课题之一。羰基、烯基和炔基等官能团已被广泛用于开发碳骨架的新转化。另一方面，重点放在酰胺的硫同源物，即硫酰胺。探讨了硫酰胺反应物质的生成及其在碳-碳成键反应中的应用。通过含硫阴离子进行碳-碳成键反应硫酰胺与两种当量的BuLi在℃-rt下反应顺利，生成硫酰胺离子。氧环烷与硫胺离子的开环选择性地发生在与硫胺离子的氮原子相邻的碳原子上，随后发生水解反应以再生硫羰基。将该反应应用于多种氧环烷，并给出了最有用的化合物之一1,3-氨基醇和氧杂嗪的合成方法。通过含硫阳离子物质形成碳-碳键的反应硫胺与MeOTf的甲基化在几秒钟内完成，得到硫胺盐。然后，在得到的硫胺盐中加入乙酰化锂和有机镁试剂。结果表明，叔原基胺具有较高的效率和选择性。此外，还实现了在硫胺盐上添加有机锌乙基醚，从而生成具有炔骨架的叔胺。总之，在研究中使用的物种是从硫酰胺衍生出来的，它们很容易从市售材料中制备。在此基础上，建立了现有方法不易得到的有价值衍生物的新合成路线。