Nitrene transfer reactions by late transition metal complexes

This thesis presents nitrene transfer reactions that are catalyzed or mediated by late transition metal complexes. Sterically large, fluorinated supporting ligands are used to minimize potential side reactions. A new 1,10-phenanthroline ligand has been synthesized with 2,4,6-(CF3)3C6H2- groups in the 2- and 9-positions (1). A cationic copper(l) complex of 1 catalyzes nitrene transfer from N-(p-toluenesulfonylimino)phenyliodinane (PhlNTs) to the C-H bonds of 1,3-dimethoxybenzene in 63% yield. Altering the stoichiometry results in the formation of a different major product, N,N-bis(2',4'-dimethoxyphenyl)-p-toluenesulfonamide, in 33% yield. Treatment of a cationic copper(l) complex of 1 with p-nitrobenzenesulfonyl azide (NsN3) results in the formation of a rare mononuclear sulfonamido complex of copper(ll), 2. This complex is presumably formed via decomposition of a reactive sulfonimido complex of copper(lll). Although not a proficient nitrene transfer reagent to benzene, complex 2 is a precatalyst for nitrene transfer from NsN3 to benzene. Deprotonation of a palladium(ll) sulfonamido complex of 1 results in the formation of the first mononuclear sulfonimido complex of palladium,

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2007

Author dc:creator

• Hamilton, Charles W., Ph. D. Massachusetts Institute of Technology

Advisor dc:contributor.advisor

• Joseph P. Sadighi.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

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

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/38618

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/38618