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Lithiation of a Silyl Ether: Formation of an ortho-Fries Hydroxyketone


  • We thank Academia Sinica and Ministry of Science and Technology (Taiwan) for financial support and MS lab of the Institute of Chemistry, Academia Sinica for mass analysis.


A hydroxy-directed alkylation of an N,N-diethylarylamide using CIPE-assisted α-silyl carbanions (CIPE=complex-induced proximity effect) has been developed using a simple reagent combination of LDA (lithium diisopropylamide) and chlorosilane. A study of the mechanism, and the application of the procedure to an anionic Snieckus–Fries rearrangement for a highly efficient synthesis of the potent phosphatidylinositol 3-kinase (PI3K) inhibitor LY294002, are reported.

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