Phosphine oxides as stabilizing ligands for the palladium-catalyzed cross-coupling of potassium aryldimethylsilanolates

Scott E. Denmark; Russell C. Smith; Steven A. Tymonko

doi:10.1016/j.tet.2007.02.017

Phosphine oxides as stabilizing ligands for the palladium-catalyzed cross-coupling of potassium aryldimethylsilanolates

Scott E. Denmark, Russell C. Smith, Steven A. Tymonko

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The palladium-catalyzed cross-coupling reaction of potassium (4-methoxyphenyl)dimethylsilanolate (K⁺1^-) with aryl bromides has been demonstrated using triphenylphosphine oxide as a stabilizing ligand. Unsymmetrical biaryls can be prepared from a variety of aryl bromides in good yield with short reaction times. Qualitative kinetic studies compared effects of different phosphine oxides on the rate of cross-coupling and established the beneficial effect of these ligands in the reaction of electron-rich arylsilanolates. The improved yield and reproducibility of the cross-coupling of several bromides was demonstrated by direct comparison of reactions performed with and without triphenylphosphine oxide under non-rigorous exclusion of oxygen.

Original language	English (US)
Pages (from-to)	5730-5738
Number of pages	9
Journal	Tetrahedron
Volume	63
Issue number	26
DOIs	https://doi.org/10.1016/j.tet.2007.02.017
State	Published - Jun 25 2007

Keywords

Biaryls
Cross-coupling
Phosphine oxides
Silanols

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

Online availability

10.1016/j.tet.2007.02.017

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title = "Phosphine oxides as stabilizing ligands for the palladium-catalyzed cross-coupling of potassium aryldimethylsilanolates",

abstract = "The palladium-catalyzed cross-coupling reaction of potassium (4-methoxyphenyl)dimethylsilanolate (K+1-) with aryl bromides has been demonstrated using triphenylphosphine oxide as a stabilizing ligand. Unsymmetrical biaryls can be prepared from a variety of aryl bromides in good yield with short reaction times. Qualitative kinetic studies compared effects of different phosphine oxides on the rate of cross-coupling and established the beneficial effect of these ligands in the reaction of electron-rich arylsilanolates. The improved yield and reproducibility of the cross-coupling of several bromides was demonstrated by direct comparison of reactions performed with and without triphenylphosphine oxide under non-rigorous exclusion of oxygen.",

keywords = "Biaryls, Cross-coupling, Phosphine oxides, Silanols",

author = "Denmark, {Scott E.} and Smith, {Russell C.} and Tymonko, {Steven A.}",

note = "Funding Information: We are grateful to the National Institutes of Health for generous financial support (GM 63167). R.C.S. acknowledges the University of Illinois for a graduate fellowship. S.A.T. thanks Johnson and Johnson PRI for a graduate fellowship. ",

year = "2007",

month = jun,

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doi = "10.1016/j.tet.2007.02.017",

language = "English (US)",

volume = "63",

pages = "5730--5738",

journal = "Tetrahedron",

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publisher = "Elsevier Limited",

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T1 - Phosphine oxides as stabilizing ligands for the palladium-catalyzed cross-coupling of potassium aryldimethylsilanolates

AU - Denmark, Scott E.

AU - Smith, Russell C.

AU - Tymonko, Steven A.

N1 - Funding Information: We are grateful to the National Institutes of Health for generous financial support (GM 63167). R.C.S. acknowledges the University of Illinois for a graduate fellowship. S.A.T. thanks Johnson and Johnson PRI for a graduate fellowship.

PY - 2007/6/25

Y1 - 2007/6/25

N2 - The palladium-catalyzed cross-coupling reaction of potassium (4-methoxyphenyl)dimethylsilanolate (K+1-) with aryl bromides has been demonstrated using triphenylphosphine oxide as a stabilizing ligand. Unsymmetrical biaryls can be prepared from a variety of aryl bromides in good yield with short reaction times. Qualitative kinetic studies compared effects of different phosphine oxides on the rate of cross-coupling and established the beneficial effect of these ligands in the reaction of electron-rich arylsilanolates. The improved yield and reproducibility of the cross-coupling of several bromides was demonstrated by direct comparison of reactions performed with and without triphenylphosphine oxide under non-rigorous exclusion of oxygen.

AB - The palladium-catalyzed cross-coupling reaction of potassium (4-methoxyphenyl)dimethylsilanolate (K+1-) with aryl bromides has been demonstrated using triphenylphosphine oxide as a stabilizing ligand. Unsymmetrical biaryls can be prepared from a variety of aryl bromides in good yield with short reaction times. Qualitative kinetic studies compared effects of different phosphine oxides on the rate of cross-coupling and established the beneficial effect of these ligands in the reaction of electron-rich arylsilanolates. The improved yield and reproducibility of the cross-coupling of several bromides was demonstrated by direct comparison of reactions performed with and without triphenylphosphine oxide under non-rigorous exclusion of oxygen.

KW - Biaryls

KW - Cross-coupling

KW - Phosphine oxides

KW - Silanols

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U2 - 10.1016/j.tet.2007.02.017

DO - 10.1016/j.tet.2007.02.017

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AN - SCOPUS:34248634279

SN - 0040-4020

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SP - 5730

EP - 5738

JO - Tetrahedron

JF - Tetrahedron

IS - 26

ER -

Phosphine oxides as stabilizing ligands for the palladium-catalyzed cross-coupling of potassium aryldimethylsilanolates

Abstract

Keywords

ASJC Scopus subject areas

Online availability

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