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Journal of the Mexican Chemical Society
versión impresa ISSN 1870-249X
J. Mex. Chem. Soc vol.53 no.3 Ciudad de México jul./sep. 2009
Article
Stereochemical Studies on the Addition of Allylsilanes to Aldehydes. The SE' Component*
Scott E. Denmark* and Neil G. Almstead
245 Roger Adams Laboratory, Box 18, Department of Chemistry, University of Illinois, 600 S. Mathews Ave., Urbana, IL 61801, Phone:(217) 3330066, Fax: (217) 3333984, *Responsible author: sdenmark@illinois.edu.
Received August 14, 2009
Accepted September 30, 2009
Abstract
Model compounds ul 1 and lk1 have been studied to determine both the position of the silicon electrofuge and the relative orientation of the double bonds in the transition structure of the allylmetalaldehyde condensation. The use of the deuterium label allows an unbiased assessment of the syn versus anti SE' pathways. The synthesis of configurational proof of model systems ul1 and lk1 are discussed as well as the cyclization of the model system. Cyclization of model 1 was found to proceed with high selectivity via an anti SE' pathway regardless of the proximal/distal ratio for all Lewis acids studied. Reactions promoted by fluoride ion favored the proximal product, but both syn and anti pathways were observed.
Key words: Allyllsilanes, Addition to Aldehides, Condensation Reaction, Cyclization, Stereochemistry.
Resumen
Se estudiaron los compuestos modelo ul1 y lk1 para determinar tanto la posición del silicio electrofugo como la orientación relativa de los dobles enlaces en el estado de transición de la condensación alilmetalaldehído. El uso del marcaje con deuterio permite una evaluación adecuada de los mecanismos syn versus anti SE'. Se describe la síntesis de los compuestos modelo wl1 y lk1 , así como se discute el proceso de ciclación de dichos compuestos. Se encontró que la ciclación de los compuestos modelo 1 procede con elevada selectividad vía un mecanismo SE', independientemente de la proporción de los productos proximal/distal que se obtengan y de los ácidos de Lewis estudiados. Las reacciones promovidas por el ion fluoruro favorecen el producto proximal, aunque ambos caminos syn y anti fueron observados.
Palabras clave: Alilsilanos, adición a aldehídos, reacción de condensación, ciclización, esteroquímica.
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Acknowledgement
We gratefully acknowledge the financial support from the National Science Foundation (NSF CHE 8818147 and 9121631) for this research.
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*Dedicated to the memory of Ernest L. Eliel, the doyen of stereochemistry.