A Facile Synthesis of Chiral Phosphinoaryloxazolines

doi:10.11944/j.issn.1000-0518.2018.02.170066

Chinese Journal of Applied Chemistry ›› 2018, Vol. 35 ›› Issue (2): 189-196.DOI: 10.11944/j.issn.1000-0518.2018.02.170066

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A Facile Synthesis of Chiral Phosphinoaryloxazolines

CAO Baochen^a^b,WU Guojie^b^c^*(),HE Yupeng^a^*(),HAN Fushe^b

^aCollege of Chemistry,Chemical Engineering and Environmental Engineering,Liaoning Shihua University,Fushun,Liaoning 113001,China
^bKey Laboratory of Synthetic Rubber,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun,Jilin 130022,China
^cEngineering Research Center of Marine Biological Resource Comprehensive Utilization,Third Institute of Oceanography,State Oceanic Administration,Xiamen,Fujian 361005,China

Received:2017-03-10 Accepted:2017-05-03 Published:2018-02-01 Online:2018-01-29
Contact: WU Guojie,HE Yupeng
Supported by:
Supported by the National Natural Science Foundation of China(No.21602215), the Fund of the Engineering Research Center of Marine Bioresources Comprehensive Utilization, SOA(No.MBRCU201604)

Abstract

Abstract:

As a widely used class of privileged ligands, phosphinoaryloxazolines(PHOX) have attracted much attention from chemists. However, the previous synthetic methods have problems of long steps, low yield and difficult separation and so on. In this article, a simple and efficient procedure for the synthesis of phosphinoaryloxazolines(PHOX) has been developed. First, 2-(diphenylphosphino)benzoic acid was condensed with various enantiomerically pure amino alcohols in the presence of 1-hydroxylbenzotriazole(HOBt) and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride(EDCI) in dimethylformamide to give the corresponding (amido alcohol)s amides in excellent yields. Then the (amido alcohol)s amides were subjected to the oxazoline ring formation by treatment with triphenylphosphine, triethylamine and carbon tetrachloride in acetonitrile to afford a series of phosphinooxazolines in 64%86% total yields. Subsequently, (S)-t-BuPHOX was applied in the palladium-catalyzed decarboxylative Tsuji allylations of β-ketoester, giving an excellent isolated yield of 80% with an enantiomeric excess of 84%. The new synthetic procedure has the advantages of using readily available starting materials, mild reaction conditions, and high overall yields.

Key words: phosphinooxazolines, (diphenyl-phosphino)benzoic acid, chiral amino alcohols

CAO Baochen, WU Guojie, HE Yupeng, HAN Fushe. A Facile Synthesis of Chiral Phosphinoaryloxazolines[J]. Chinese Journal of Applied Chemistry, 2018, 35(2): 189-196.

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A Facile Synthesis of Chiral Phosphinoaryloxazolines

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