Stereocontrol in Nucleophilic Substitution Reactions at Silicon: The Role of Permutation in Generating Silicon-Centered Chirality

Intramolecular isomerization in pentacoordinate
compounds can play
an essential role for the adjustment of defined stereochemical information.
Here, we present a conclusive mechanism of a stereocontrolled reaction
on chiral dimethoxysilanes that opens new aspects in understanding
the origin of creating silicon-centered chirality during a nucleophilic
substitution process. By combining experimental, structural, and quantum
chemical methods, we were able to disclose an interconversion process,
based on consecutive Berry-type motions, as the most plausible mechanism
for describing the stereochemical outcome in suchlike substitution
reactions.