Electrophilic Cyanation of Alkenyl Tosylates, Ketones and Amines using Disubstituted Malononitriles

This thesis describes new methods for the synthesis of alkenyl nitriles, β-ketonitriles, andcyanamides using various disubstituted malononitriles as electrophilic cyanation reagents. These approaches may be of interest to workers attempting to access compounds of those types. Chapter 1 provides a brief overview of the thesis topics and compares nucleophilic to electrophilic cyanation. Chapter 2 describes a novel method for the construction of alkenyl nitriles from alkenyl tosylates using disubstituted malononitriles as electrophilic cyanating reagents under reductive nickel catalysis. Chapter 3 describes a novel method for the synthesis of β-ketonitriles from ketones and disubstituted malononitriles under basic conditions. Several β-ketoenamines were found to be produced using similar conditions, and their synthesis is also elaborated. Chapter 4 describes continued efforts related to the synthesis cyanamides using disubstituted malononitriles under basic conditions. A novel ortho-functionalization of the cyanating reagent byproduct was observed during reaction optimization.

Department dc:contributor.department

Chemistry

Year dc:date.issued

2025

Author dc:creator

• Graham, Joshua Morgan

Advisor dc:contributor.advisor

• Rousseaux, Sophie

Handle dc:identifier.uri

https://hdl.handle.net/1807/142658

OAI identifier oai:identifier

oai:utoronto.scholaris.ca:1807/142658