Palladium- and nickel-catalyzed C-N cross-coupling reactions featuring soluble organic bases

Chapter 1: Breaking the Base Barrier: An Electron-Deficient Palladium Catalyst Enables the Use of a Common Soluble Base in C-N Coupling Due to the low intrinsic acidity of amines, palladium-catalyzed C-N cross-coupling plagued continuously by the necessity to employ strong, inorganic, or insoluble bases. To surmount the many Due to the low intrinsic acidity of amines, palladium-catalyzed C-N crosscoupling has been practical obstacles associated with these reagents, we utilized a commercially available dialkyl triarylmonophosphine-supported palladium catalyst that facilitates a broad range of C-N coupling reactions in the presence of weak, soluble bases. The mild and general reaction conditions show extraordinary tolerance for even highly base-sensitive functional groups. Additionally, insightful heteronuclear NMR studies using ⁻¹⁵N-labeled amine complexes provide evidence for the key acidifying effect of the cationic palladium center.

Name thesis:degree_name

Doctoral

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2020

Author dc:creator

• Dennis, Joseph Michael,Jr.

Advisor dc:contributor.advisor

• Stephen L. Buchwald.

• Chemistry.

Statement dc:rights

• MIT theses may be protected by copyright. Please reuse MIT thesis content according to the MIT Libraries Permissions Policy, which is available through the URL provided.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

https://hdl.handle.net/1721.1/128408

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/128408