Part I. Large scale procedure for the α-arylation of esters catalyzed by the pd(i) dimer [p(tbu)3]pd(μ-br)]2. Part II. Palladium-catalyzed γ-arylation of α,β-unsaturated esters

We report the development of a procedure for the α-arylation of esters on 42 mmol scale which did not require use of a glovebox. The coupling of 3-bromoanisole and methyl isobutyrate catalyzed by 0.075 % [(P(tBu)3Pd(μ-Br)]2 occurred in 72% yield. The reaction was performed with commercially available reagents at a lab bench utilizing Schlenk technique. We report the γ-arylation of α,β-unsaturated esters in high yield with broad scope by coupling aryl, heteroaryl and vinyl halides with the corresponding silicon dienolates. These reactions occur in high yield with a variety of esters and with aromatic and vinylic electrophiles bearing potentially reactive functional groups. The coupling also proceeds in moderate to good yield for the coupling with silyl ketene acetals containing substitution at the α,β,γ- or δ-position. Moreover, these reactions occur without typical fluoride activators.

Name thesis:degree_name

M.S.

Level thesis:degree_level

Thesis

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2010

Author dc:creator

• Huang, David S.

Contributors dc:contributor

• Hartwig, John F.

• cross-coupling
• enolates
• homogeneous catalysis
• palladium

Statement dc:rights

• Copyright 2010 David S. Huang

Language dc:language

en

Handle dc:identifier

http://hdl.handle.net/2142/16816

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/16816