title: Lithiation of a silyl ether: formation of an ortho-Fries hydroxyketone.
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.
authors: 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.
authors: Hong-Jay
authors: HJ
authors: Lo
authors: Chin-Yin
authors: CY
authors: Lin
authors: Mei-Chun
authors: MC
authors: Tseng
authors: Rong-Jie
authors: RJ
authors: Chein
keywords: alkylation; hydroxyketones; rearrangement; synthetic methods; α-silyl carbanions