Synthesis of enantiopure homoallylic ethers by reagent controlled facial selective allylation of chiral ketones.
The stereoselective allylation of chiral methyl ketones to give tertiary homoallylic ethers, which can easily be transformed into homoallylic alcohols, is described. Reaction of the enantiopure ketones 8a-d and the racemic ketones 26a-d with the norpseudoephedrine derivative 2 or ent-2 and allylsilane in the presence of a catalytic amount of trifluoromethanesulfonic acid, led to a series of homoallylic ethers with good to excellent diastereoselectivity (85:15 to > 97:3). The allylation is reagent controlled and nearly independent from the stereogenic centers in the substrates. A partial kinetic resolution was observed using the racemic ketones 26a-d. In the reaction of the chiral ketones 8a-d with the achiral reagents ethoxytrimethylsilane and allylsilane only a low diastereoselectivity was observed.
Tietze
L F
LF
Institut für Organische Chemie, Georg-August-Universität Göttingen, Germany. ltietze@gwdg.de
Weigand
B
B
Völkel
L
L
Wulff
C
C
Bittner
C
C