Stereocontrolled Syntheses of Functionalized cis- and trans-Siladecalins

Abstract

We report the synthesis of both diastereomers of an all-silicon analog of decalin. Carbocyclic decalin is a ubiquitous bicyclic structural motif. The siladecalin synthesis provides materials functionalized with either Si-Ph or Si-H groups, versatile entry points for further chemical diversification. The synthesis of silicon-stereogenic silanes is significantly less precedented than the synthesis of asymmetric carbon centers, and strategies for control of relative stereochemistry in oligosilanes are hardly described. This study offers insights of potential generality, such as the epimerization of the cis-isomer to the thermodynamically downhill trans-isomer via a hypothesized pentavalent intermediate. Decalin is a classic example in the conformational analysis of organic ring systems, and the carbocyclic diastereomers have highly divergent conformational profiles. Like the carbocycle, we observe different conformational properties in cis- and trans-siladecalins with consequences for NMR spectroscopy, optical properties, and vibrational spectroscopy. This study showcases the utility of targeted synthesis for preparing complex and functionalized polycyclic silanes.