Regioselective, Nucleophilic Activation of C-F Bonds in o-Fluoroanilines

Reactions of fluorinated anilines with stoichiometric Ti(NMe2)4 in mesitylene (typically for 23 h at 120 °C) afforded moderate to high yields of the corresponding N,N-dimethyl-o-phenylenediamine derivatives resulting from defluoroamination of a fluorine atom ortho to the NH2 of the starting aniline. Reactivity increased with additional ring fluorination in general accordance with established regiochemical (activating and deactivating) trends. Based on results, we propose a metal-mediated, SNAr-based mechanism. We report the scope and limitations of this reaction and discuss trends in reactivity according to a putative mechanistic scheme.

Name thesis:degree_name

Master of Science

Level thesis:degree_level

masters

Discipline thesis:degree_discipline

Chemistry

Department dc:contributor.department

Chemistry

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2019

Author dc:creator

• Hough, Sarita Elizabeth

Chair dc:contributor.committeechair

• Deck, Paul A.

Committee members dc:contributor.committeemember

• Dorn, Harry C.
• Morris, Amanda J.
• Merola, Joseph S.

• titanium amide
• SNAr
• defluorination
• anilines
• organometallic
• nucleophiles

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

vt_gsexam:20323

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/90657