Stereoselective Synthesis of Silicon‐Stereogenic Aminomethoxysilanes: Easy Access to Highly Enantiomerically Enriched Siloxanes

A route towards the synthesis of N,O‐functionalized silicon‐stereogenic organosilanes with excellent optical purities has been developed. Investigations into the stereoconvergence and configurational stability of an aminomethoxysilane suggest a kinetically controlled multistep substitution mechanism. Selective exchange of the Si‐N bond by a second Si‐O bond builds the basis for the controlled formation of chiral siloxane units with different oxygen‐containing functional groups. Subsequent reactions of the chiral aminomethoxysilanes with hydroxy groups support a general inversion mechanism at the asymmetrically substituted silicon atom of N,O‐functionalized organosilanes.