Title:
KINETIC RESOLUTION OF ASYMMETRIC CATALYTIC HYDROGENATION OF RACEMIC Δ-HYDROXY ESTER AND APPLICATION THEREOF
Document Type and Number:
WIPO Patent Application WO/2016/082583
Kind Code:
A1
Abstract:
The present invention relates to kinetic resolution of asymmetric catalytic hydrogenation of racemic δ-hydroxy ester and an application thereof. An iridium catalyst of a chiral spiropyridine amidocyanogen phosphin ligand is used; in a condition in which an alkali exists, asymmetric catalytic hydrogenation is performed on a racemic δ-hydroxy ester, to obtain a chiral δ-hydroxy ester and 1,5-glycol having particular optical purity. The method is a new, efficient, highly selective, economical, desirably operable, and environmentally friendly method suitable for industrial production. An optically active chiral δ-hydroxy ester and 1,5-glycol can be obtained at very high enantioselectivity and yield with relatively low usage of a catalyst. The chiral δ-hydroxy ester and 1,5-glycol obtained by using the method can be used as a critical chiral raw material for asymmetrical synthesis of a chiral drug (R)-lisofylline and a natural product (+)-civet, (-)-indolizidine 167B, and alkali (-)-coniine.
Inventors:
ZHOU QILIN (CN)
XIE JIANHUA (CN)
YANG XIAOHUI (CN)
WANG LIXIN (CN)
XIE JIANHUA (CN)
YANG XIAOHUI (CN)
WANG LIXIN (CN)
Application Number:
PCT/CN2015/086425
Publication Date:
June 02, 2016
Filing Date:
August 08, 2015
Export Citation:
Assignee:
ZHEJIANG JIUZHOU PHARM CO LTD (CN)
International Classes:
C07C67/48; C07C29/149; B01J31/24; C07C31/20; C07C33/26; C07C69/675; C07C69/708; C07C69/732; C07D309/30
Domestic Patent References:
| WO2012065571A1 | 2012-05-24 |
Foreign References:
| CN104355997A | 2015-02-18 | |||
| CN102040625A | 2011-05-04 | |||
| CN201410714176A | 2014-11-28 | |||
| CN102040625A | 2011-05-04 |
Other References:
YANG, X.H. ET AL.: "Remote Ester Group Leads to Efficient Kinetic Resolution of Racemic Aliphatic Alcohols via Asymmetric Hydrogenation.", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 136, no. 50, 1 December 2014 (2014-12-01), pages 17426, XP055445820, ISSN: 0002-7863
XIE, J.H. ET AL.: "An Additional Coordination Group Leads to Extremely Efficient Chiral Iridium Catalysts for Asymmetric Hydrogenation of Ketones.", ANGEWANDTE CHEMIE INTERNATIONAL EDITION., vol. 50, no. 32, 12 July 2011 (2011-07-12), pages 7329 - 7332, XP055060237, ISSN: 1521-3773
DE VRIES, J. G.ELSEVIER, C. J.: "The Handbook of Homogeneous Hydrogenation", 2007, WILEY-VCH
ZHAO, B.HAN, Z.DING, K., ANGEW. CHEM., INT. ED., vol. 52, 2013, pages 4744
XIE, J.-H.ZHOU, Q.-L., ACTA CHIM. SINICA, vol. 70, 2012, pages 1427
OHKUMA, T.SANDOVAL, C. A.SRINIVASAN, R.LIN, Q.WEI, Y.MUNIZ, K.NOYORI, R., J. AM. CHEM. SOC., vol. 127, 2005, pages 8288
VEDEJS, E.JURE, M., ANGEW. CHEM. INT. ED., vol. 44, 2005, pages 3974
PELLISSIER, H., ADV. SYNTH. CATAL., vol. 353, 2011, pages 1613
XIE, J.-H.LIU, X.-Y.XIE, J.-B.WANG, L.-X.ZHOU, Q.-L., ANGEW. CHEM., INT. ED., vol. 50, 2011, pages 7329
XIE, J.H. ET AL.: "An Additional Coordination Group Leads to Extremely Efficient Chiral Iridium Catalysts for Asymmetric Hydrogenation of Ketones.", ANGEWANDTE CHEMIE INTERNATIONAL EDITION., vol. 50, no. 32, 12 July 2011 (2011-07-12), pages 7329 - 7332, XP055060237, ISSN: 1521-3773
DE VRIES, J. G.ELSEVIER, C. J.: "The Handbook of Homogeneous Hydrogenation", 2007, WILEY-VCH
ZHAO, B.HAN, Z.DING, K., ANGEW. CHEM., INT. ED., vol. 52, 2013, pages 4744
XIE, J.-H.ZHOU, Q.-L., ACTA CHIM. SINICA, vol. 70, 2012, pages 1427
OHKUMA, T.SANDOVAL, C. A.SRINIVASAN, R.LIN, Q.WEI, Y.MUNIZ, K.NOYORI, R., J. AM. CHEM. SOC., vol. 127, 2005, pages 8288
VEDEJS, E.JURE, M., ANGEW. CHEM. INT. ED., vol. 44, 2005, pages 3974
PELLISSIER, H., ADV. SYNTH. CATAL., vol. 353, 2011, pages 1613
XIE, J.-H.LIU, X.-Y.XIE, J.-B.WANG, L.-X.ZHOU, Q.-L., ANGEW. CHEM., INT. ED., vol. 50, 2011, pages 7329
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