Abstract
The Brook rearrangement of simple, chiral tertiary benzylic α‐hydroxysilanes is presented. The rearrangement followed by proton trapping is enantiospecific and proceeds with inversion of the configuration at the carbon center. Importantly, the [1,2]‐Brook rearrangement can be followed by trapping of methyl or allyl electrophiles even in the protic environment, although with minimal retention of chirality.
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