Catalytic Group Transfer with Late Metal Nitrenes

后金属氮烯的催化基团转移

• 批准号: 0716304
• 负责人: Timothy Warren
• 金额: $ 42万
• 依托单位: Georgetown University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-09-01 至 2010-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0716304&HistoricalAwards=false
• 关键词: Catalytic; Group; Transfer; Late; Metal

Professor Timothy Warren of Georgetown University is supported by the Inorganic, Bioinorganic and Organometallic Chemistry program to develop catalysts for promoting nitrene insertion into C-H bonds and nitrene addition across olefins. This proposal utilizes bulky beta-diketiminato copper and nickel complexes as catalysts with organoazides as the nitrene source. Current methods limit the nature of the nitrene substituent to strongly electron withdrawing groups, and moving to other nitrene sources will expand the range of applications available to this powerful tool. In addition to insertion of nitrenes into C-H bonds, efforts to add nitrene fragments to olefins, carbon monoxide, and isocyanide are being pursued. Discrete metal-nitrene complexes that can be isolated and characterized play a central role in this chemistry.Both the conversion of hydrocarbons into amines and the conversion of olefins into aziridines are synthetically challenging, high value-added transformations. The broader impacts of this project include exposing students to sophisticated experimental techniques suitable for probing reaction mechanisms in catalytic organometallic transformations.

乔治城大学的Timothy Warren教授在无机、生物无机和金属有机化学项目的支持下，开发了用于促进氮烯插入C-H键和氮烯跨烯烃加成的催化剂。该方案利用体积较大的β-二酮亚胺铜镍络合物作为催化剂，以有机叠氮化合物作为氮源。目前的方法将氮基的性质限制为强吸电子基团，而转移到其他氮源将扩大这一强大工具的应用范围。除了将氮烯插入C-H键之外，还在努力将氮化物碎片添加到烯烃、一氧化碳和异氰化物中。可以分离和表征的离散金属-氮化物在这种化学中起着核心作用。碳氢化合物转化为胺和烯烃转化为氮杂环丙烷都是合成上具有挑战性的高附加值转化。这个项目的更广泛的影响包括让学生接触到适合于探索催化有机金属转化中的反应机理的复杂的实验技术。