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Donor/Acceptor‐Stabilized 1‐Silaketene: Reversible [2+2] Cycloaddition with Pyridine and Evolution by an Olefin Metathesis Reaction
Author(s) -
Reyes Morelia Lopez,
Troadec Thibault,
Rodriguez Ricardo,
Baceiredo Antoine,
SaffonMerceron Nathalie,
Branchadell Vicenç,
Kato Tsuyoshi
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601753
Subject(s) - chemistry , cycloaddition , intramolecular force , pyridine , aldehyde , olefin fiber , medicinal chemistry , photochemistry , metathesis , acyclic diene metathesis , stereochemistry , catalysis , organic chemistry , polymerization , polymer
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.