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.

乔治敦大学的蒂莫西·沃伦（Timothy Warren）教授得到了无机，生物无机和有机金属化学计划的支持，旨在开发催化剂，以促进硝基插入到整个烯烃中的C-H键中，并添加硝基。该建议利用笨重的β-二氨酸铜和镍复合物作为硝酸盐来源的催化剂。当前的方法将硝基取代基的性质限制为强烈的电子撤回组，而转移到其他硝酸盐来源将扩大该功能强大工具可用的应用范围。除了将硝酸盐插入C-H键中，还在追求将硝基碎片添加到烯烃，一氧化碳和异氰化物中。 可以隔离和表征的离散金属硝基络合物在这种化学中起着核心作用。碳氢化合物转化为胺，烯烃转化为氮杂胺，在综合中具有挑战性，高增值转换。该项目的更广泛的影响包括使学生了解适用于催化有机金属转化中反应机制的复杂实验技术。