Sugar-derived Amine Catalyzed Intramolecular Aldol Reactions.

摘要

In this thesis, the background information on aminocatalysis is introduced. A review regarding Jorgensen-Hayashi type diarylprolinol silyl ether catalysts is presented.;4-hydroxylated 1,7-dial 70 was synthesized via alkylation, dihydroxylation and glycol cleavage. The symmetrical dial was prepared as a precursor to construct optically active hydroxylated cyclohexane 101a,b and as a platform to test the stereoselectivities of the prepared amine catalysts in a facile manner.;Seven new chiral hydroxylated amine catalysts (105, 131, 134, 146, 154, 157 and 160) bearing different aromatic groups and 2,3-O protecting groups were synthesized from D-arabinose following established protocol. These catalysts were applied in asymmetric intramolecular aldol reaction and amine 134 (90%, 93% ee) and 157 (94%, 89% ee) displayed positive results.;The absolute configurations of aldol adduct (ƒy)-101a and (ƒy)-101b were sucessfully assigned by comparing to established literature work of a similar reaction.;A series of chiral hydroxylated enones were synthesized from D-glucose as anticancer COTC analogues following established procedures. Their cytotoxicities against normal and cancer cell lines were measured and discussed.