Stereochemical Studies on the Addition of Allylsilanes to Aldehydes. The S_E' 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) 333–0066, Fax: (217) 333–3984, ^*Responsible author: sdenmark@illinois.edu.

Received August 14, 2009
Accepted September 30, 2009

Abstract

Model compounds ul –1 and lk–1 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 allylmetal–aldehyde condensation. The use of the deuterium label allows an unbiased assessment of the syn versus anti S_E' pathways. The synthesis of configurational proof of model systems ul–1 and lk–1 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 S_E' 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 ul–1 y lk–1 para determinar tanto la posición del silicio electrofugo como la orientación relativa de los dobles enlaces en el estado de transición de la condensación alilmetal–aldehído. El uso del marcaje con deuterio permite una evaluación adecuada de los mecanismos syn versus anti S_E'. Se describe la síntesis de los compuestos modelo wl–1 y lk–1 , 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 S_E', 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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Note

^*Dedicated to the memory of Ernest L. Eliel, the doyen of stereochemistry.