INTRAMOLECULAR NITROGEN INSERTION: A METHODOLOGY FOR THE ISOLATION OF SUBSTITUTED AZIRIDINE RING SYSTEMS

Author

Jesse Dean Singer Small, Bard CollegeFollow

Date of Submission

Spring 2016

Academic Programs and Concentrations

Chemistry

Project Advisor 1

Emily McLaughlin

Abstract/Artist's Statement

Intramolecular aziridination remains a novel method for the creation of three-membered heterocyclic ring systems for the creation of new C-N bonds within complex organic molecules. In these reactions, a source of nitrogen, notably the carbamate functional group, is oxidized to a nitrene, after which it inserts into a nearby alkene, forming a new bicyclic ring system. This ring system includes the aziridine structure, which is then a suitable target for nucleophilic ring opening from a variety of reagents. Such reactions proceed efficiently under microwave irradiation in the presence of hypervalent iodine oxidizing agents, along with a rhodium acetate dimer catalyst, but are subject to unwanted cleavage of the aziridine ring structure caused by byproducts of the reaction conditions, namely the acetic acid from the oxidizing agent. Using an indole backbone and attaching a carbamate functionality to the 3-position carbon, we attempt to develop a methodology for the isolation of the aziridine structure for use in C-N bond formation in complex organic syntheses. Experimentation consists of the use of different oxidizing agents to eliminate the emersion of acidic byproducts, as well as the addition of other reagents e.g. mild bases to neutralize these byproducts.

Access Agreement

On-Campus only

Creative Commons License

This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 4.0 License.

Recommended Citation

Small, Jesse Dean Singer, "INTRAMOLECULAR NITROGEN INSERTION: A METHODOLOGY FOR THE ISOLATION OF SUBSTITUTED AZIRIDINE RING SYSTEMS" (2016). Senior Projects Spring 2016. 68.
https://digitalcommons.bard.edu/senproj_s2016/68