924961-36-4Relevant articles and documents
Two-directional elaboration of hydroxyacetone under thermodynamically controlled conditions: Allylation or 2-propynylation and aldol reaction
Ishikawa, Teruhiko,Aikawa, Toshiaki,Ohata, Eiko,Iseki, Takako,Maeda, Satoshi,Matsuo, Takashi,Fujino, Tatsuo,Saito, Seiki
, p. 435 - 441 (2007/10/03)
Enolate generated from O-(tetrahydropyran-2-yl)hydroxyacetone under thermodynamically controlled conditions (1.3 equiv of NaH, THF, 0 °C to rt) was allylated at the carbon bearing the protected hydroxy group with very high regioselectively. When tert-BuOH, equivalent to the excessive portion of initially added NaH, was introduced into the mixture followed by addition of aldehyde, aldol reaction took place on the methyl group to give 1-substituted 4-hydroxy-(1E),6-heptadien-3-one in acceptable yields after acidic treatment of the mixture for dehydration and deprotection. Introducing a chiral auxiliary protecting group into hydroxyacetone led to asymmetric allylation though stereoselectivity was around 50% ee. Thus, the hidden aspect of the chemoselective nature of protected hydroxy acetone-derived enolate generated under thermodynamically controlled conditions has opened a new avenue for two-directional elaboration of hydroxyacetone that should be potentially useful in organic synthesis.
