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1999.9 - 2003.6 Nankai University, College of Chemistry, B. S.
2003.9 - 2009.6 Nankai University, SKLEOC, Ph. D.
Chiral alcohols are important intermediates in organic synthesis, natural products, and chiral drugs. However, the synthetic methods of chiral primary alcohol are limited to lipase-catalyzed resolution of racemic alcohols, and few catalytic processes. This thesis describes a catalytic asymmetric hydrogenation dynamic kinetic resolution of -substituted aldehydes to afford chiral primary alcohols with good to high enantioselectivites.
SDP-Ru-diamine complexes are efficient catalyst in asymmetric hydrogenation of prochiral -substituted alkylaldehydes, producing β-aryl primary alcohols. By optimization of ligands, temperature and other conditions, a variety of -aryl aldehydes can be hydrogenated to primary alcohols with up to 5000 TON, 100% yield and 96% ee. A mechanism was proposed to explain the enantiocontrol in the reaction. (S)-Fenvaleric acid and Bay 1005 were synthesized by using SDPs-Ru-diamine catalyzed asymmetric hydrogenation of -aryl aldehydes as a key step.
With the same catalysts α-aryloxy alkylaldehydes were hydrogenated as well. The ee value is up to 80%. Chiral β-aryloxyalcohols are important intermediates. This study provided the first example of catalytic asymmetric synthesis of β-aryloxy primary alcohols.
Using the asymmetric hydrogenation of α-[4-piperdine]-arylacetaldehyde as a key step, chiral drugs 3-aryl-quinuclidines and MCH antagonist were synthesized..
Keywords: hydrogenation, asymmetric catalysis, ruthenium, primary alcohols, diphosphine ligands, diamine
1.Zhang-Tao Zhou, Jian-Hua Xie, Qi-Lin Zhou*, Enantioselective synthesis of chiral β-aryloxy alcohols by asymmetric hydrogenation of β-aryloxy aldehydes via dynamic kinetic resolution, Adv. Synth. Catal. 2009, 351, 363-366.
2.Jian-Hua Xie, Zhang-Tao Zhou, Wei-Ling Kong, Qi-Lin Zhou*, Ru-Catalyzed asymmetric hydrogenation of racemic aldehydes via dynamic kinetic resolution: efficient synthesis of optically active primary alcohols, J. Am. Chem. Soc. 2007,129, 1868-1869.