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

Huang, David S.

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https://hdl.handle.net/2142/16816 Copy

Description

Title

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

Author(s)

Huang, David S.

Issue Date

2010-08-20T17:58:44Z

Director of Research (if dissertation) or Advisor (if thesis)

Hartwig, John F.

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

M.S.

Degree Level

Thesis

Keyword(s)

• cross-coupling
• enolates
• homogeneous catalysis
• palladium

Abstract

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.

Graduation Semester

2010-08

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

Copyright and License Information

Copyright 2010 David S. Huang

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