权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

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.

发展和发现新的高选择性、高效率的合成反应是有机合成化学中的重要问题之一。官能团如羰基、烯基和炔基已被广泛用于开发碳骨架的新转化。另一方面，重点放在酰胺的硫异构体上，即，硫代酰胺。探索了硫代酰胺反应物种的生成及其在碳-碳键形成反应中的应用。硫代酰胺与2当量BuLi的反应在℃ ~室温下顺利进行，生成硫代酰胺二价阴离子。环氧乙烷与硫代酰胺双阴离子的开环选择性地发生在与双阴离子的氮原子相邻的碳原子处，然后通过水解处理再生硫代羰基。将该反应应用于各种环氧乙烷，并提供了最有用的化合物之一1，3-氨基醇和恶嗪的合成方法。通过含硫阳离子物种的碳-碳键形成反应硫代酰胺与MeOTf的甲基化在几秒钟内完成，得到硫代亚胺盐。然后，将乙炔锂和有机镁试剂加入到所得硫代亚胺鎓盐中。结果，以高效率和高选择性获得了具有新碳骨架的叔炔丙胺。此外，还实现了将有机锌乙炔化物加成到硫代亚胺盐上，从而得到具有烯炔骨架的叔胺。总之，研究中使用的物种来自硫代酰胺，其易于由市售材料制备。在此基础上，建立了新的合成路线，得到了用已知方法不易得到的有价值的衍生物。