1,1-Disilyl alcohols as d1 synthons: Harnessing the 1,2-Brook rearrangement

Article abstract of DOI:10.1002/1522-2675(200210)85:10<3349::AID-HLCA3349>3.0.CO;2-K

1,1-Disilyl alcohols like 6 give the silyl ethers like 9 on treatment with base and alkyl halides, in a reaction which may be formulated as the alkylation of the Brook-rearranged carbanion 8. The products can be oxidised to give ketones like 10, showing that this Brook-rearranging system supplies a controlled d¹ synthon of the acyl anion class. The alcohols can be prepared from the acid chloride 12 and dimethyl(phenyl)silyllithium, but the intermediate anion 21 need not be worked up; it can be used directly in the alkylation step.