847151-91-1Relevant articles and documents
Catalytic electronic activation as a tool for the addition of stabilised nucleophiles to allylic alcohols
Black, Phillip J.,Edwards, Michael G.,Williams, Jonathan M.J.
, p. 1363 - 1374 (2007/10/03)
This paper describes the activation of 2-cyclohexen-1-ol (1) and 2-cyclopenten-1-ol (11) through the use of aluminium-catalysed transfer hydrogenation. The electronically activated substrates are demonstrated to undergo facile conjugate addition and, when the alcohol functional group is subsequently restored in a one-pot procedure, this leads to an indirect addition of nucleophiles to allylic alcohols. This novel methodology has been termed catalytic electronic activation. The aluminium tert-butoxide catalysed conversion of 2-cyclohexen-1-ol (1) into 2-(3-hydroxycyclohexyl)-2- methylmalononitrile (18) and 2-cyclopenten-1-ol (11) into 2-(3- hydroxycyclopentyl)-2-methylmalononitrile (16) in 90 and 60% yield, respectively has been demonstrated through an efficient domino Oppenauer/Michael addition/Meerwein-Ponndorf-Verley process.