87(P-22) 触媒的不斉Baylis-Hillman反応の開発とその天然物合成への活用(ポスター発表の部)

概要

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Development of a simple and reliable method for the construction of multifunctional molecules starting from readily available starting materials is of great importance in synthetic organic chemistry. In this regard, the Baylis-Hillman reaction, tertiary amine-catalyzed C-C bond-forming reaction of an aldehyde with an acrylate, has attracted considerable attention. We have recently discovered a reliable asymmetric Baylis-Hillman reaction, which utilizes (3R,8R,9S)-10,11-dihydro-3,9-epoxy-6'-hydroxy-cinchonane (β-cupreidine) as a chiral amine catalyst and 1,1,1,3,3,3-hexafluoroisopropyl acrylate as an activated alkene. This method allows conversion of a wide variety of aldehydes to the corresponding (R)-(α-methylene-β-hydroxy)esters with high enantiomeric excess in reasonable yields. We describe here the structure-function relationship of the amine catalyst as well as the scope and limitation of the reaction. We also present the preliminary result on the synthesis of a new catalyst, which acts as a pseudo-enantiomer of β-cupreidine to give (S)-(α-methylene-β-hydroxy)esters. Furthermore, we discuss enantio-, and stereocontrolled syntheses of mycestericin E and epopromycin B, biologically interesting natural products, by stereoselective functionalization of the Baylis-Hillman adducts.
天然有機化合物討論会の論文
2002-09-01