Catalytic C-N and C-F bond formation by organometallic group 11 complexes

This thesis presents a study of the reaction between an (NHC)gold(I) fluoride complex (NHC = N-heterocyclic carbene) and alkynes (Chapter 1). Gold(I) and fluoride add trans across the triple bond of 3-hexyne and 1-phenyl-l-propyne to form (fluorovinyl)gold(I) complexes, with exclusive geminal arrangement between the phenyl group and gold in the latter case. This addition is reversible, and the (fluorovinyl)gold(I) complexes can extrude alkyne to return (NHC)gold(I) fluoride. Treatment of (fluorovinyl)gold(I) complexes with strong acid protonates the vinylic group with strong acid to afford trans-hydrofluorination. The same fluoroalkene product is obtained by treatment of an (1i2-alkyne)gold(I) complex with the mild HF source Et3N.3HF. Cationic (NHC)gold(I) complexes catalyze the trans-hydrofluorination of internal alkynes with Et3N*3HF (Chapter 2). Sterically demanding, electrophilic supporting ligands and the presence of acid buffers improve reaction efficiency. A study of aryl-substituted alkynes suggests that electron-poor aryl groups favor shorter reaction times and higher regioselectivity of fluorination. A heavily fluorinated phenanthroline ligand supporting a cationic copper(I) catalyst allows efficient functionalization of C-H bonds using sulfonyl azides (Chapter 3).

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

• Akana, Jennifer Anne

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/1721.1/39585

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/39585