Citation: 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. doi: 10.11944/j.issn.1000-0518.2018.02.170066 shu

A Facile Synthesis of Chiral Phosphinoaryloxazolines

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

a.
College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning Shihua University, Fushun, Liaoning 113001, China
b.
Key Laboratory of Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022, China
c.
Engineering Research Center of Marine Biological Resource Comprehensive Utilization, Third Institute of Oceanography, State Oceanic Administration, Xiamen, Fujian 361005, China

Corresponding author: WU Guojie, gjwu@ciac.ac.cn HE Yupeng, yupeng.he@lnpu.edu.cn
Received Date: 10 March 2017
Revised Date: 12 April 2017
Accepted Date: 3 May 2017

Fund Project: 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)the Fund of the Engineering Research Center of Marine Bioresources Comprehensive Utilization, SOA MBRCU201604the National Natural Science Foundation of China 21602215

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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.
- phosphinooxazolines,
- (diphenyl-phosphino)benzoic acid,
- chiral amino alcohols
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