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Robust and Efficient, Yet Uncatalyzed, Synthesis of Trialkylsilyl-Protected Cyanohydrins from Ketones

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Fabien L. Cabirol,^†^‡ Angela E. C. Lim,^† Ulf Hanefeld,^‡ Roger A. Sheldon,^‡ and Ilya M. Lyapkalo*^§

Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, S(627833), Singapore, Institute of Organic Chemistry and Biochemistry, Flemingovo n. 2., 166 10 Prague 6, Czech Republic, and Biocatalysis and Organic Chemistry, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands ilya.lyapkalo@uochb.cas.cz

J. Org. Chem., 2008, 73 (6), pp 2446–2449

DOI: 10.1021/jo702587e

Publication Date (Web): February 29, 2008

Abstract

High-yielding cyanosilylation of ketones with NaCN and various chlorotrialkylsilanes in DMSO proceeds smoothly without catalysis to give silyl-protected ketone cyanohydrins. The unique role of DMSO consists in rendering naked cyanide anions that reversibly add to the CO bond at the rate-determining step followed by fast trapping of the transient tertiary sodium cyanoalcoholates with chlorotrialkylsilanes or in situ generated cyanotrialkylsilanes. Preparatively, the reaction matches the best known catalytic cyanosilylation systems applying expensive Me₃SiCN and demonstrates unprecedented efficiency in the synthesis of sterically congested trialkylsilyl-protected cyanohydrins.

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Published In Issue March 21, 2008
Received December 4, 2007

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Robust and Efficient, Yet Uncatalyzed, Synthesis of Trialkylsilyl-Protected Cyanohydrins from Ketones

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Recommend & Share

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Cooperative Thiourea–Brønsted Acid Organocatalysis: Enantioselective Cyanosilylation of Aldehydes with TMSCN

Chiral Allene-Containing Phosphines in Asymmetric Catalysis

Gram-Scale Synthesis of the A′B′-Subunit of Angelmicin B

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