The properties of bridged polycyclic silanes with [2.2.1] silabicycloheptene cores  have been little studied, despite the potential of these structures as reactive intermediates for the synthesis of densely-substituted cyclohexenes and related heterocycles.  The strain inherent to these compounds derives from compression of the C-Si-C bond angle brought on by the position of the silicon as the bridging atom in the [2.2.1] bicycloheptene motif.  Long-term development and adoption of methods utilizing substituted bridged polycyclic silanes in organic synthesis requires a thorough understanding of their stabilities and reactivity patterns.  The synthesis of structurally-diverse bridged polycyclic silanes via Diels-Alder cycloadditions of 2,4-disubstituted, 2,5-disubstituted, and 3,4-disubstituted siloles will be described.  The relationship between substitution pattern and susceptibility to hydrolytic ring opening will be discussed, and the abilities of both alkyl and aryl groups to direct the regioselectivity of ring opening will be examined.   Preliminary results from further reactivity screening will also be presented, focusing on the formation of carbon-carbon bonds.<br/>

Bridged polycyclic silanes: Structure-reactivity studies for the development of synthetic applications

251st National Meeting (2016)

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