CAREER: Generation of Cyanocarbenes from Alkynes and Azides

在这个项目中，北卡罗来纳大学格林斯伯勒分校化学和生物化学系的Mitchell P.Croatt教授得到了化学系化学结构、动力学和机制B计划的资助，以研究由炔和叠氮化物制成的氰卡宾的合成和反应。该项目的目标是使用容易获得的化合物，让它们经历以前从未探索过的反应机制，并产生分子复杂性显著增加的产品。这个项目的一个教育目标是开发一个项目，帮助学生更好和更快地学习有机化学，训练他们想象分子，就像他们是经验丰富的有机化学家一样。该项目旨在创造一种游戏般的氛围，使学习有机化学变得有趣，同时也帮助学生更有效地学习材料。最后，将通过包括一系列讨论小组在内的各种方法积极开展对未被充分代表的少数群体研究人员的培训。该项目探索将亲电炔和亲核叠氮化物转化为氰卡宾，然后研究它们随后的反应活性。亲电的炔烃，高价的三氟化碘，是可分离的。然而，这个项目将在原位形成它们，并允许它们与叠氮阴离子反应。生成一系列活性中间体，包括亚乙基卡宾和炔基叠氮化物，最终生成氰卡宾。这些亲电的卡宾将被允许与各种亲核试剂反应，产生额外的活性中间体，这些中间体可以经过广泛的重排，然后产生分子复杂性显着增加的稳定分子。

For this project, Professor Mitchell P. Croatt in the Department of Chemistry and Biochemistry at the University of North Carolina at Greensboro is funded by the Chemical Structure, Dynamics and Mechanisms B Program of the Chemistry Division to investigate the synthesis and reactions of cyanocarbenes made from alkynes and azides. The goal of the project is to use readily available compounds, have them undergo previously unexplored reaction mechanisms, and generate products with significantly increased molecular complexity. An educational goal of this project is to develop a program to help students learn organic chemistry better and more quickly train them to visualize molecules as if they were experienced organic chemists. The program is designed to create a game-like atmosphere to make learning organic chemistry fun while also helping students to learn the material more efficiently. Finally, training of underrepresented minority researchers will actively take place through a variety of methods including a series of discussion panels.This project explores the conversion of electrophilic alkynes and nucleophilic azides to cyanocarbenes and then studies their subsequent reactivity. The electrophilic alkynes, hypervalent iodonium alkynyl triflates, are isolable. However, this project will form them in situ and allow them to react with azide anions. A series of reactive intermediates, including vinylidene carbenes and alkynyl azides, are formed, and eventually cyanocarbenes are generated. These electrophilic carbenes will be allowed to react with a variety of nucleophiles to produce additional reactive intermediates which can undergo extensive rearrangement before producing stable molecules with significantly increased molecular complexity.