DEVELOPMENT OF NEW SYNTHETIC REACTIONS BY USING THE PROPERTIES OF SELENOCARBONYL GROUP

利用硒代羰基的性质开发新的合成反应

基本信息

批准号：
12650852
负责人：
MURAI Toshiaki
金额：
$ 2.11万
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：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

项目摘要

The development of new synthetic reactions with high efficiency and selectivity is one of the most important issues in synthetic organic chemistry. The acceleration and reduction of synthetic process from the starting materials to the final products are also of important. A variety of reactions utilizing the ability of double bonds involving the carbon atoms have been known. If the compounds bearing the weak double bonds with the carbon atom are designed and easily handled, unprecedented synthetic reactions under milder reaction conditions for shorter reaction times would be realized. The prime objective of the present research was to explore synthetic reactions on the basis of the higher reactivity of the double bonds between the carbon atom and the selenium atom, which was found in the forth law of the periodic table of elements.As a result, the use of selenium isologues of amides, i.e., selenoamides provided new types of reactions, and their scope and limitations were disclosed as follows.・Addition reaction of selenium isologues of enolate ions, i.e., eneselenolates to aldehydes smoothly proceeded to give b-hydroxy selenoamides. The selenoamides bearing benzyl groups on the nitrogen atom exhibited high stereoselectivity.・Methylation of selenoamides with methyl triflate was complete within one sec to produce selenoiminium salts. The alkynylation of selenoiminium salts took place to give α,β-unsaturated ketones in good to high yields.・The reaction of α-silyl selenoacetamides with aldehydes furnished α,β-unsaturated selenoamdies with E-selectivity. The application of this reaction led to selenoamides bearing long olefinic groups.

以高效率和选择性的发展是新的合成反应的发展是合成有机化学中最重要的问题之一。从起始材料到最终产品的合成过程的加速和减少也很重要。已经知道利用涉及碳原子的双键能力的各种反应。如果设计并易于处理碳原子的弱双键的化合物，则将实现在米勒反应条件下的前所未有的合成反应，以较短的反应时间。 The prime objective of the present research was to explore synthetic reactions on the basis of the higher reaction of the double bonds between the carbon atom and the selenium atom, which was found in the forth law of the periodic table of elements.As a result, the use of selenium isologues of amides, i.e., selenoamides provided new types of reactions, and their scope and limitations were disclosed as follows.・Addition reaction of selenium isolates of enolate离子，即，烯烯丙基对醛进行平滑的醛，从而产生B-羟基硒酰胺。在氮原子上含有苄基的硒酰胺暴露于高立体选择性。・在一秒钟内完成了用三裂甲基甲基甲基酰胺的甲基化，以产生硒膜盐。发生了硒酰亚胺盐的藻类化，以良好至高产量的α，β-不饱和酮的酮。该反应的应用导致硒酰胺具有长烯烃基团。