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

Figures(2)

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
1. [1]
  Sprinz J, Helmchen G. Phosphinoaryl-and Phosphinoalkyl Oxazolines as New Chiral Ligands for Enantioselective Catalysis:Very High Enantioselectivity in Palladium Catalyzed Allylic Substitutions[J]. Tetrahedron Lett, 1993,34(11):1769-1772. doi: 10.1016/S0040-4039(00)60774-8
2. [2]
  von Matt P, Pfaltz A. Chiral Phosphinoaryldihydrooxazoles as Ligands in Asymmetric Catalysis:Pd-Catalyzed Allylic Substitution[J]. Angew Chem Int Ed, 1993,32(4):566-568. doi: 10.1002/(ISSN)1521-3773
3. [3]
  Dawson G J, Frost C, Williams J M J. Asymmetric Palladium Catalysed Allylic Substitution Using Phosphorus Containing Oxazoline Ligands[J]. Tetrahedron Lett, 1993,34(19):3149-3150. doi: 10.1016/S0040-4039(00)93403-8
4. [4]
  Helmchen G, Pfaltz A. Phosphinooxazolines——A New Class of Versatile, Modular P, N-Ligands for Asymmetric Catalysis[J]. Acc Chem Res, 2000,33(6):336-345. doi: 10.1021/ar9900865
5. [5]
  Bausch C C, Pfaltz A. PHOX Ligands. Privileged Chiral Ligands and Catalysts[M]. Wiley-VCH Verlag GmbH & Co. KgaA, 2006:221-256.
6. [6]
  Hargaden G C, Guiry P J. Recent Applications of Oxazoline-Containing Ligands in Asymmetric Catalysis[J]. Chem Rev, 2009,109(6):2505-2550. doi: 10.1021/cr800400z
7. [7]
  Carroll M P, Guiry P J. P, N Ligands in Asymmetric Catalysis[J]. Chem Soc Rev, 2014,43(3):819-833. doi: 10.1039/C3CS60302D
8. [8]
  Allen J V, Dawson G J, Frost C G. Preparation of Novel Sulfur and Phosphorus Containing Oxazolines as Ligands for Asymmetric Catalysis[J]. Tetrahedron, 1994,50(3):799-808. doi: 10.1016/S0040-4020(01)80795-X
9. [9]
  Gant T G, Meyers A I. The Chemistry of 2-Oxazolines(1985 present)[J]. Tetrahedron, 1994,50(8):2297-2360. doi: 10.1016/S0040-4020(01)86953-2
10. [10]
  Koch G, Lloyd-jones G C, Loiseleur O. Synthesis of Chiral (Phosphinoaryl) Oxazolines, a Versatile Class of Ligands for Asymmetric Catalysis[J]. Recl Trav Chim Pays-Bas, 1995,114(4/5):206-210.
11. [11]
  Peer M, de Jong J C, Kiefer M. Preparation of Chiral Phosphorus, Sulfur and Selenium Containing 2-Aryloxazolines[J]. Tetrahedron, 1996,52(21):7547-7583. doi: 10.1016/0040-4020(96)00267-0
12. [12]
  Tani K, Behenna D C, McFadden R M. A Facile and Modular Synthesis of Phosphinooxazoline Ligands[J]. Org Lett, 2007,9(13):2529-2531.
13. [13]
  Sedinkin S L, Rath N P, Bauer E B. Synthesis and Structural Characterization of New Phosphinooxazoline Complexes of Iron[J]. J Organomet Chem, 2008,693(18):3081-3091. doi: 10.1016/j.jorganchem.2008.06.031
14. [14]
  Wu W Q, Peng Q, Dong D X. A Dramatic Switch of Enantioselectivity in Asymmetric Heck Reaction by Benzylic Substituents of Ligands[J]. J Am Chem Soc, 2008,130(30):9717-9725. doi: 10.1021/ja7104174
15. [15]
  Marinho V R, Rodrigues A I, Burke A J. Novel Chiral P, O-Ligands for Homogeneous Pd(0) Catalysed Asymmetric Allylic Alkylation Reactions[J]. Tetrahedron:Asymmetry, 2008,19(4):454-458. doi: 10.1016/j.tetasy.2008.01.024
16. [16]
  Zhu S F, Xie J B, Zhang Y Z. Well-Defined Chiral Spiro Iridium/Phosphine-Oxazoline Cationic Complexes for Highly Enantioselective Hydrogenation of Imines at Ambient Pressure[J]. J Am Chem Soc, 2006,128(39):12886-12891. doi: 10.1021/ja063444p
17. [17]
  Zhang X P, Liang H Y, Cao Z K. Enantioselective Synthesis of Axially Chiral Biaryl Monophosphine Oxides via Direct Asymmetric Suzuki Coupling and DFT Investigations of the Enantioselectivity[J]. ACS Catal, 2014,4(5):1390-1397. doi: 10.1021/cs500208n
18. [18]
  Burrell G, Evans J M, Jones G E. The Action of Diethylaminosulphur Trifluoride(dast) on Trans-4-Amido-3-chromanols:Preparation of cis-Amidoalcohols via Oxazolines[J]. Tetrahedron Lett, 1990,31(25):3649-3652. doi: 10.1016/S0040-4039(00)94467-8
19. [19]
  Vorbrüggen H, Krolikiewicz K. A Simple Synthesis of Δ²-Oxazolines, Δ²-Oxazines, Δ²-Thiazolines and Δ²-Imidazolines[J]. Tetrahedron Lett, 1981,22(45):4471-4474. doi: 10.1016/S0040-4039(01)93017-5
20. [20]
  Meyers A I, Hoyer D. Stereochemistry of the Ph₃P-CCl₄ Mediated Cyclization of Carboxylic Acids and 1, 2-Amino Alcohols(Vorbruggen Method)[J]. Tetrahedron Lett, 1985,26(39):4687-4690. doi: 10.1016/S0040-4039(00)94924-4
21. [21]
  Vorbrüggen H, Krolikiewicz K. A Simple Synthesis of Δ²-Oxazines, Δ²-Oxazines, Δ²-Thiazolines and 2-Substituted Benzoxazoles[J]. Tetrahedron, 1993,49(41):9353-9372. doi: 10.1016/0040-4020(93)80021-K
22. [22]
  Robert A Craig Ⅱ, Steven A Loskot, Brian M Stoltz. Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones[J]. Org Lett, 2015,17(21):5160-5163. doi: 10.1021/acs.orglett.5b02376
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