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 -