CAREER: Generation of Cyanocarbenes from Alkynes and Azides

在这个项目中，北卡罗莱纳大学格林斯博罗分校化学与生物化学系的Mitchell P. Croatt教授得到了化学学部化学结构、动力学和机制B项目的资助，研究了由炔和叠氮化物制成的氰碳烯的合成和反应。该项目的目标是使用现成的化合物，让它们经历以前未探索的反应机制，并产生具有显着增加的分子复杂性的产品。这个项目的一个教育目标是开发一个程序，帮助学生更好地学习有机化学，更快地训练他们像有经验的有机化学家一样可视化分子。该课程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，对代表性不足的少数民族研究人员的培训将通过包括一系列讨论小组在内的各种方法积极进行。本项目探索亲电炔和亲核叠氮化物转化为三羧基，并研究其后续反应活性。亲电炔，高价炔基三氟酸碘，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。形成一系列反应中间体，包括偏乙烯基碳烯和炔基叠氮化合物，最终生成三聚氰碳烯。这些亲电性碳烯将被允许与各种亲核试剂反应以产生额外的反应中间体，这些中间体在产生具有显著增加分子复杂性的稳定分子之前可以经历广泛的重排。

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.