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2000.9 - 2004.7 Yunnan University, B. S.
2004.9 - 2007.6 Nankai University, SKLEOC, M. S.
Address: HongyunHonghe Tobacco Group, No.181 Hongjin Road, Kunming, Yunnan, 650202 China
Asymmetric hydrogenation of racemic a-substituted ketones via dynamic kinetic resolution (DKR) is an elegant method to synthesize chiral compounds contained two or more stereogenic centers. However, the successful substrates are limited to a-aryl, a-alkyl, a-alkoxycycloketones. Thus, the asymmetric hydrogenation of a-substituted acyclic dialkylketones is still a challenge subject.
In this thesis, Ru(Ⅱ)-SDPs/diamine catalyzed asymmetric hydrogenation of the racemic a-alkyl substituted arylacetones via DKR have been developed. Good to excellent syn/anti stereoselectivity (up to 97:3) and high enantioselectivity (up to 97% ee) for syn-isomer were achieved. Using this method (2R,3S)-4-(3,4-dichlorophenyl)-3-(2-fluoro-4-biphenyl)butan-2-ol, a key intermediate for the synthesis of J-104,118, was synthesized.
The synthesis of chiral 1,2-aminoalcohols by using asymmetric hydrogenation of a-dialkylamino substituted arylacetones via DKR was also achieved. Using RuCl2-(S)-SDP/(R,R)-DPEN as catalyst, excellent anti-diastereoselectivities (> 99:1) and enantioselectivities (up to 100% ee) for anti isomer were obtained.
In this study, 39 new compounds were synthesized and identified by 1H NMR, 13C NMR, elmento-analysis or HRMS analysis.
Keywords: a-substituted alkylketones, catalytic asymmetric hydrogenation, dynamic kinetic resolution (DKR), Ru(Ⅱ)-SDPs/diamine catalyst
1.Jian-Βo Xie, Jian-Hua Xie*, Xiao-Yan Liu, Wei-Ling Kong, Shen Li, and Qi-Lin Zhou*, Highly enantioselective hydrogenation of α-arylmethylene cycloalkanones catalyzed by iridium complexes of chiral spiro aminophosphine ligands, J. Am. Chem. Soc. 2010, 132, 4538-4539.
2.Sheng Liu, Jian-Hua Xie, Wei Li, Wei-Ling Kong, Li-Xin Wang, Qi-Lin Zhou*, Highly enantioselective synthesis of chiral cyclic amino alcohols and conhydrine by ruthenium-catalyzed asymmetric hydrogenation, Org. Lett. 2009, 11, 4994-4997.
3.Jian-Hua Xie, Wei-Ling Kong, Xiao-Cheng Wang, Wen-Ju Bai, Li-Xin Wang, Qi-Lin Zhou*, Chiral ruthenium-SDPs/diamine complexes-catalyzed enantioselective hydrogenation of α-alkyl arylacetones via dynamic kinetic resolution, Front. Chem. China 2009, 4, 299-306.
4.Jian-Hua Xie, Sheng Liu, Wei-Ling Kong, Wen-Jun Bai, Xiao-Chen Wang, Li-Xin Wang, Qi-Lin Zhou*, Highly enantioselective and diastereoslective synthesis of chiral amino alcohols by ruthenium-catalyzed asymmetric hydrogenation of α-amino aliphatic ketones, J. Am. Chem. Soc. 2009, 131, 4222-4223.
5. 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.