Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene

Tom G. Driver; K. A. Woerpel

doi:10.1021/ja0306563

Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene

Tom G. Driver, K. A. Woerpel

Chemistry

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

Abstract

Kinetic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes in the presence of 5 mol % of (Ph₃P) ₂AgOTf suggested a possible mechanism for silver-mediated di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 was determined to be one. Inverse kinetic saturation behavior (rate inhibition) was observed in monosubstituted alkene and cyclohexene concentrations. Saturation kinetic behavior in catalyst concentration was observed. A reactive intermediate, a silyisilver complex, was observed using low temperature ²⁹Si NMR spectroscopy. Competition experiments between substituted styrenes and a deficient amount of 1 correlated well with the Hammett equation and provided a p value of -0.62 ± 0.02 using σ_p constants. These data support a mechanism involving reversible silver-promoted di-tert-butylsilylene extrusion from 1 followed by irreversible concerted electrophilic attack of the silylsilver intermediate on the alkene.

Original language	English (US)
Pages (from-to)	9993-10002
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	126
Issue number	32
DOIs	https://doi.org/10.1021/ja0306563
State	Published - Aug 18 2004

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/ja0306563

Cite this

@article{da8ad49397604b6d97c1984e33cf3479,

title = "Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene",

abstract = "Kinetic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes in the presence of 5 mol % of (Ph3P) 2AgOTf suggested a possible mechanism for silver-mediated di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 was determined to be one. Inverse kinetic saturation behavior (rate inhibition) was observed in monosubstituted alkene and cyclohexene concentrations. Saturation kinetic behavior in catalyst concentration was observed. A reactive intermediate, a silyisilver complex, was observed using low temperature 29Si NMR spectroscopy. Competition experiments between substituted styrenes and a deficient amount of 1 correlated well with the Hammett equation and provided a p value of -0.62 ± 0.02 using σp constants. These data support a mechanism involving reversible silver-promoted di-tert-butylsilylene extrusion from 1 followed by irreversible concerted electrophilic attack of the silylsilver intermediate on the alkene.",

author = "Driver, {Tom G.} and Woerpel, {K. A.}",

year = "2004",

month = aug,

day = "18",

doi = "10.1021/ja0306563",

language = "English (US)",

volume = "126",

pages = "9993--10002",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "32",

}

TY - JOUR

T1 - Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene

AU - Driver, Tom G.

AU - Woerpel, K. A.

PY - 2004/8/18

Y1 - 2004/8/18

N2 - Kinetic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes in the presence of 5 mol % of (Ph3P) 2AgOTf suggested a possible mechanism for silver-mediated di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 was determined to be one. Inverse kinetic saturation behavior (rate inhibition) was observed in monosubstituted alkene and cyclohexene concentrations. Saturation kinetic behavior in catalyst concentration was observed. A reactive intermediate, a silyisilver complex, was observed using low temperature 29Si NMR spectroscopy. Competition experiments between substituted styrenes and a deficient amount of 1 correlated well with the Hammett equation and provided a p value of -0.62 ± 0.02 using σp constants. These data support a mechanism involving reversible silver-promoted di-tert-butylsilylene extrusion from 1 followed by irreversible concerted electrophilic attack of the silylsilver intermediate on the alkene.

AB - Kinetic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes in the presence of 5 mol % of (Ph3P) 2AgOTf suggested a possible mechanism for silver-mediated di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 was determined to be one. Inverse kinetic saturation behavior (rate inhibition) was observed in monosubstituted alkene and cyclohexene concentrations. Saturation kinetic behavior in catalyst concentration was observed. A reactive intermediate, a silyisilver complex, was observed using low temperature 29Si NMR spectroscopy. Competition experiments between substituted styrenes and a deficient amount of 1 correlated well with the Hammett equation and provided a p value of -0.62 ± 0.02 using σp constants. These data support a mechanism involving reversible silver-promoted di-tert-butylsilylene extrusion from 1 followed by irreversible concerted electrophilic attack of the silylsilver intermediate on the alkene.

UR - http://www.scopus.com/inward/record.url?scp=4043141373&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=4043141373&partnerID=8YFLogxK

U2 - 10.1021/ja0306563

DO - 10.1021/ja0306563

M3 - Article

C2 - 15303873

AN - SCOPUS:4043141373

SN - 0002-7863

VL - 126

SP - 9993

EP - 10002

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 32

ER -

Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this