当前位置：
X-MOL 学术
›
Organometallics
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Sila-Peterson Reaction of Cyclic Silanides.
Organometallics ( IF 2.5 ) Pub Date : 2020-04-28 , DOI: 10.1021/acs.organomet.0c00106 Andreas W Kyri 1 , Lukas Schuh 1 , Andreas Knoechl 1 , Michael Schalli 1 , Ana Torvisco 1 , Roland C Fischer 1 , Michael Haas 1 , Harald Stueger 1
Organometallics ( IF 2.5 ) Pub Date : 2020-04-28 , DOI: 10.1021/acs.organomet.0c00106 Andreas W Kyri 1 , Lukas Schuh 1 , Andreas Knoechl 1 , Michael Schalli 1 , Ana Torvisco 1 , Roland C Fischer 1 , Michael Haas 1 , Harald Stueger 1
Affiliation
|
Sila-Peterson type reactions of the 1,4,4-tris(trimethylsilyl)-1-metallooctamethylcyclohexasilanes (Me3Si)2Si6Me8(SiMe3)M (2a, M = Li; 2b, M = K) with various ketones were investigated. The obtained products strongly depend on the nature of the ketone component. With 2-adamantanone 2a,b afforded the moderately stable silene 3. 3 is the first example of an Apeloig–Ishikawa–Oehme-type silene with the tricoordinate silicon atom incorporated into a cyclopolysilane framework and could be characterized by NMR and UV spectroscopy as well as by trapping reactions with water, methanol, and MeLi. The reaction of 2b with aromatic ketones also follows a sila-Peterson type mechanism with formation of carbanionic species. With 1,2-diphenylcyclopropenone 2b reacted by conjugate 1,4-addition to give a spirocyclic carbanion. In most cases the underlying reaction mechanism could be elucidated by the isolation and characterization of unstable intermediates and final products after proper derivatization.
中文翻译：
环状硅烷的Sila-Peterson反应。
1,4,4-三（三甲基甲硅烷基）-1-金属八甲基甲基环六硅烷（Me 3 Si）2 Si 6 Me 8（SiMe 3）M（2a，M = Li; 2b，M = K）的Sila-Peterson型反应研究了各种酮。所获得的产物强烈取决于酮组分的性质。与2-金刚烷酮2a，b一起提供了中等稳定的硅烷3。3是Apeloig–Ishikawa–Oehme型硅烷的第一个实例，其三配位硅原子被掺入环聚硅烷骨架中，并可以通过NMR和UV光谱以及与水，甲醇和MeLi的捕集反应进行表征。的反应2b中与芳族酮也遵循与形成碳负离子物质的硅杂彼得森型机构。与1,2-二苯基环丙烯酮2b通过共轭1,4-加成反应生成螺环碳负离子。在大多数情况下，可以通过适当的衍生化后不稳定中间体和最终产物的分离和表征来阐明潜在的反应机理。
更新日期：2020-04-28
中文翻译：
环状硅烷的Sila-Peterson反应。
1,4,4-三（三甲基甲硅烷基）-1-金属八甲基甲基环六硅烷（Me 3 Si）2 Si 6 Me 8（SiMe 3）M（2a，M = Li; 2b，M = K）的Sila-Peterson型反应研究了各种酮。所获得的产物强烈取决于酮组分的性质。与2-金刚烷酮2a，b一起提供了中等稳定的硅烷3。3是Apeloig–Ishikawa–Oehme型硅烷的第一个实例，其三配位硅原子被掺入环聚硅烷骨架中，并可以通过NMR和UV光谱以及与水，甲醇和MeLi的捕集反应进行表征。的反应2b中与芳族酮也遵循与形成碳负离子物质的硅杂彼得森型机构。与1,2-二苯基环丙烯酮2b通过共轭1,4-加成反应生成螺环碳负离子。在大多数情况下，可以通过适当的衍生化后不稳定中间体和最终产物的分离和表征来阐明潜在的反应机理。
京公网安备 11010802027423号