Donor/Acceptor-Stabilized 1-Silaketene: Reversible [2+2] Cycloaddition with Pyridine and Evolution by an Olefin Metathesis Reaction

Morelia Lopez Reyes; Thibault Troadec; Ricardo Rodriguez; Antoine Baceiredo; Nathalie Saffon-Merceron; Vicenç Branchadell; Tsuyoshi Kato

doi:10.1002/chem.201601753

Donor/Acceptor-Stabilized 1-Silaketene: Reversible [2+2] Cycloaddition with Pyridine and Evolution by an Olefin Metathesis Reaction

Morelia Lopez Reyes, Thibault Troadec, Ricardo Rodriguez, Antoine Baceiredo, Nathalie Saffon-Merceron, Vicenç Branchadell, Tsuyoshi Kato

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

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Abstract

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim The reaction of silacyclopropylidene 1 with benzaldehyde generates a 1-silaketene complex 2 by a formal atomic silicon insertion into the C=O bond of the aldehyde. The highly reactive 1-silaketene 2 undergoes a reversible [2+2] cycloaddition with pyridine to give sila-β-lactam 3. Of particular interest, in the presence of 4-dimethylaminopyridine (DMAP), 1-silaketene complex 2 evolves through an intramolecular olefin metathesis reaction, generating a new 1-silaketene complex 8 and cis-stilbene. Theoretical studies suggest that the reaction proceeds through the formation of a transient silacyclobutanone, a four-membered-ring intermediate, similar to that proposed by Chauvin and co-workers for the transition-metal-based olefin metathesis.

Original language	English
Pages (from-to)	10247-10253
Journal	Chemistry - A European Journal
Volume	22
Issue number	29
DOIs	https://doi.org/10.1002/chem.201601753
Publication status	Published - 1 Jan 2016

Keywords

1-silaketene
atomic silicon insertion
olefin metathesis
silanone
transition-metal-like behavior

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10.1002/chem.201601753

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title = "Donor/Acceptor-Stabilized 1-Silaketene: Reversible [2+2] Cycloaddition with Pyridine and Evolution by an Olefin Metathesis Reaction",

abstract = "{\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim The reaction of silacyclopropylidene 1 with benzaldehyde generates a 1-silaketene complex 2 by a formal atomic silicon insertion into the C=O bond of the aldehyde. The highly reactive 1-silaketene 2 undergoes a reversible [2+2] cycloaddition with pyridine to give sila-β-lactam 3. Of particular interest, in the presence of 4-dimethylaminopyridine (DMAP), 1-silaketene complex 2 evolves through an intramolecular olefin metathesis reaction, generating a new 1-silaketene complex 8 and cis-stilbene. Theoretical studies suggest that the reaction proceeds through the formation of a transient silacyclobutanone, a four-membered-ring intermediate, similar to that proposed by Chauvin and co-workers for the transition-metal-based olefin metathesis.",

keywords = "1-silaketene, atomic silicon insertion, olefin metathesis, silanone, transition-metal-like behavior",

author = "Reyes, {Morelia Lopez} and Thibault Troadec and Ricardo Rodriguez and Antoine Baceiredo and Nathalie Saffon-Merceron and Vicen{\c c} Branchadell and Tsuyoshi Kato",

year = "2016",

month = jan,

day = "1",

doi = "10.1002/chem.201601753",

language = "English",

volume = "22",

pages = "10247--10253",

number = "29",

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TY - JOUR

T1 - Donor/Acceptor-Stabilized 1-Silaketene: Reversible [2+2] Cycloaddition with Pyridine and Evolution by an Olefin Metathesis Reaction

AU - Reyes, Morelia Lopez

AU - Troadec, Thibault

AU - Rodriguez, Ricardo

AU - Baceiredo, Antoine

AU - Saffon-Merceron, Nathalie

AU - Branchadell, Vicenç

AU - Kato, Tsuyoshi

PY - 2016/1/1

Y1 - 2016/1/1

N2 - © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim The reaction of silacyclopropylidene 1 with benzaldehyde generates a 1-silaketene complex 2 by a formal atomic silicon insertion into the C=O bond of the aldehyde. The highly reactive 1-silaketene 2 undergoes a reversible [2+2] cycloaddition with pyridine to give sila-β-lactam 3. Of particular interest, in the presence of 4-dimethylaminopyridine (DMAP), 1-silaketene complex 2 evolves through an intramolecular olefin metathesis reaction, generating a new 1-silaketene complex 8 and cis-stilbene. Theoretical studies suggest that the reaction proceeds through the formation of a transient silacyclobutanone, a four-membered-ring intermediate, similar to that proposed by Chauvin and co-workers for the transition-metal-based olefin metathesis.

AB - © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim The reaction of silacyclopropylidene 1 with benzaldehyde generates a 1-silaketene complex 2 by a formal atomic silicon insertion into the C=O bond of the aldehyde. The highly reactive 1-silaketene 2 undergoes a reversible [2+2] cycloaddition with pyridine to give sila-β-lactam 3. Of particular interest, in the presence of 4-dimethylaminopyridine (DMAP), 1-silaketene complex 2 evolves through an intramolecular olefin metathesis reaction, generating a new 1-silaketene complex 8 and cis-stilbene. Theoretical studies suggest that the reaction proceeds through the formation of a transient silacyclobutanone, a four-membered-ring intermediate, similar to that proposed by Chauvin and co-workers for the transition-metal-based olefin metathesis.

KW - 1-silaketene

KW - atomic silicon insertion

KW - olefin metathesis

KW - silanone

KW - transition-metal-like behavior

U2 - 10.1002/chem.201601753

DO - 10.1002/chem.201601753

M3 - Article

VL - 22

SP - 10247

EP - 10253

IS - 29

ER -

Donor/Acceptor-Stabilized 1-Silaketene: Reversible [2+2] Cycloaddition with Pyridine and Evolution by an Olefin Metathesis Reaction

Abstract

Keywords

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