Robust and efficient, yet uncatalyzed, synthesis of trialkylsilyl-protected cyanohydrins from ketones.
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 C double bond O 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 Me(3)SiCN and demonstrates unprecedented efficiency in the synthesis of sterically congested trialkylsilyl-protected cyanohydrins.
Cabirol
Fabien L
FL
Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, S(627833), Singapore.
Lim
Angela E C
AE
Hanefeld
Ulf
U
Sheldon
Roger A
RA
Lyapkalo
Ilya M
IM
D007659:Ketones / Q000737:chemistry*; D009570:Nitriles / Q000138:chemical synthesis*; D012821:Silanes / Q000138:chemical synthesis*
D007659:Ketones; D009570:Nitriles; D012821:Silanes; C430593:cyanohydrin