Probing the electronic demands of transmetalation in the palladium-catalyzed cross-coupling of arylsilanolates

Scott E. Denmark; Russell C. Smith; Wen Tau T. Chang

doi:10.1016/j.tet.2011.03.066

Probing the electronic demands of transmetalation in the palladium-catalyzed cross-coupling of arylsilanolates

Scott E. Denmark
, Russell C. Smith
, Wen Tau T. Chang

Chemistry

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

Abstract

The electronic characteristics of coupling partners in the transmetalation step for the cross-coupling reaction of arylsilanolates have been investigated. The ability to interrogate the transmetalation event by in situ preparation of the arylpalladium(II) silanolate intermediate has enabled a Hammett analysis for both the aryl electrophile and arylsilanolate to be conducted. These studies reveal that electron-donating groups on the silicon nucleophile and electron-withdrawing groups on the electrophile accelerate the transmetalation process.

Original language	English (US)
Pages (from-to)	4391-4396
Number of pages	6
Journal	Tetrahedron
Volume	67
Issue number	24
DOIs	https://doi.org/10.1016/j.tet.2011.03.066
State	Published - Jun 17 2011

Keywords

Cross-coupling
Hammett relationship
Mechanism
Organosilicon
Transmetalation

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

Online availability

10.1016/j.tet.2011.03.066

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title = "Probing the electronic demands of transmetalation in the palladium-catalyzed cross-coupling of arylsilanolates",

abstract = "The electronic characteristics of coupling partners in the transmetalation step for the cross-coupling reaction of arylsilanolates have been investigated. The ability to interrogate the transmetalation event by in situ preparation of the arylpalladium(II) silanolate intermediate has enabled a Hammett analysis for both the aryl electrophile and arylsilanolate to be conducted. These studies reveal that electron-donating groups on the silicon nucleophile and electron-withdrawing groups on the electrophile accelerate the transmetalation process.",

keywords = "Cross-coupling, Hammett relationship, Mechanism, Organosilicon, Transmetalation",

author = "Denmark, \{Scott E.\} and Smith, \{Russell C.\} and Chang, \{Wen Tau T.\}",

note = "We are grateful to the National Institutes of Health ( GM-63167 ) for financial support and to Johnson Matthey and Strem for gifts of palladium catalysts. R.C.S. thanks the Aldrich Chemical Company for a Graduate Student Innovation Award and Amgen for a Graduate Fellowship. W.-T.T.C acknowledges the University of Illinois for a graduate fellowship.",

year = "2011",

month = jun,

day = "17",

doi = "10.1016/j.tet.2011.03.066",

language = "English (US)",

volume = "67",

pages = "4391--4396",

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T1 - Probing the electronic demands of transmetalation in the palladium-catalyzed cross-coupling of arylsilanolates

AU - Denmark, Scott E.

AU - Smith, Russell C.

AU - Chang, Wen Tau T.

N1 - We are grateful to the National Institutes of Health ( GM-63167 ) for financial support and to Johnson Matthey and Strem for gifts of palladium catalysts. R.C.S. thanks the Aldrich Chemical Company for a Graduate Student Innovation Award and Amgen for a Graduate Fellowship. W.-T.T.C acknowledges the University of Illinois for a graduate fellowship.

PY - 2011/6/17

Y1 - 2011/6/17

N2 - The electronic characteristics of coupling partners in the transmetalation step for the cross-coupling reaction of arylsilanolates have been investigated. The ability to interrogate the transmetalation event by in situ preparation of the arylpalladium(II) silanolate intermediate has enabled a Hammett analysis for both the aryl electrophile and arylsilanolate to be conducted. These studies reveal that electron-donating groups on the silicon nucleophile and electron-withdrawing groups on the electrophile accelerate the transmetalation process.

AB - The electronic characteristics of coupling partners in the transmetalation step for the cross-coupling reaction of arylsilanolates have been investigated. The ability to interrogate the transmetalation event by in situ preparation of the arylpalladium(II) silanolate intermediate has enabled a Hammett analysis for both the aryl electrophile and arylsilanolate to be conducted. These studies reveal that electron-donating groups on the silicon nucleophile and electron-withdrawing groups on the electrophile accelerate the transmetalation process.

KW - Cross-coupling

KW - Hammett relationship

KW - Mechanism

KW - Organosilicon

KW - Transmetalation

UR - https://www.scopus.com/pages/publications/79957496157

UR - https://www.scopus.com/pages/publications/79957496157#tab=citedBy

U2 - 10.1016/j.tet.2011.03.066

DO - 10.1016/j.tet.2011.03.066

M3 - Article

C2 - 21731114

AN - SCOPUS:79957496157

SN - 0040-4020

VL - 67

SP - 4391

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JO - Tetrahedron

JF - Tetrahedron

IS - 24

ER -

Probing the electronic demands of transmetalation in the palladium-catalyzed cross-coupling of arylsilanolates

Abstract

Keywords

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