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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650852/
• 关键词: selenoamides; lithium eneselenoates; selenoiminium salts; α-sily selenoamides; α,β-unsaturated selenoamides; マイケル付加反応

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.

开发高效、高选择性的新型合成反应是有机合成化学的重要课题之一。加速和减少从起始材料到最终产品的合成过程也很重要。利用涉及碳原子的双键的能力的各种反应是已知的。如果设计和容易处理带有与碳原子的弱双键的化合物，将在更温和的反应条件下实现前所未有的合成反应，缩短反应时间。本研究的主要目的是探索基于碳原子和硒原子之间的双键的较高反应性的合成反应，这在元素周期表的第四定律中发现。因此，使用酰胺的硒异构体，即，硒代酰胺提供了新的反应类型，其范围和限制如下所述。烯醇化物离子的硒异构体的加成反应，即，烯硒烯醇化物顺利地转化为醛，得到β-羟基硒代酰胺。氮原子上带有苄基的硒代酰胺具有很高的立体选择性。硒代酰胺与三氟甲磺酸甲酯的甲基化在一秒内完成，以产生硒代亚胺鎓盐。硒亚胺盐的炔基化反应以良好到高产率得到α，β-不饱和酮。α-甲硅烷基硒代乙酰胺与醛反应，得到了具有E-选择性的α，β-不饱和硒代酰胺。该反应的应用导致带有长烯基的硒代酰胺。

项目成果

O.Niyomura: "The first alkali metal selenothioates : synthesis and molecular structure"Chem. Lett.. 968-969 (2001)

O.Niyomura：“第一种碱金属硫代硒酸盐：合成和分子结构”Chem。

T. Murai, S. Hayakawa, S. Kato: "Ammonium eneselenolates : stereochemistry and electronic properties"J. Org. Chem.. 66. 8101-8105 (2001)

T. Murai、S. Hayakawa、S. Kato：“烯烯醇酸铵：立体化学和电子特性”J。

T. Murai: "Ammonium eneselenolates : stereochemistry and electronic properties"J. Org. Chem.. 66. 8101-8105 (2001)

T. Murai：“烯烯醇酸铵：立体化学和电子特性”J。

T.Murai: "MeOTf-mediated alkynylation of selenoamides leading to β-methylselenenyl α,β-unsaturated ketones and their characterization"Org. Lett.. 3(13). 1993-1995 (2001)

T.Murai：“MeOTf 介导的硒代酰胺的炔基化生成 β-甲基硒基 α,β-不饱和酮及其表征”Org. 3(13) (2001)。

T. Murai, Y. Mutoh, S. Kato: "MeOTf-mediated alkynylation of selenoamides leading to β-methylselenenyl α,β-unsaturated ketones and their characterization"Org. Lett.. 3(13). 1993-1995 (2001)

T. Murai、Y. Mutoh、S. Kato：“MeOTf 介导的硒代酰胺的炔基化生成 β-甲基硒基 α,β-不饱和酮及其表征”Org. 3(13) (2001)。