Lithiation of a Silyl Ether: Formation of an ortho‐Fries Hydroxyketone |
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| Authors: | Dr Hong‐Jay Lo M?Sc Chin‐Yin Lin Dr Mei‐Chun Tseng Prof Rong‐Jie Chein |
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| Affiliation: | Institute of Chemistry, Academia Sinica, 128 Academia Road Sec. 2, Nankang Taipei 11529 (Taiwan) http://www.chem.sinica.edu.tw/faculty/index.php?piName=rjchein |
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| Abstract: | 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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| Keywords: | α ‐silyl carbanions alkylation hydroxyketones rearrangement synthetic methods |
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