Synlett 2017; 28(12): 1432-1436
DOI: 10.1055/s-0036-1588983
letter
© Georg Thieme Verlag Stuttgart · New York

Catalytic Synthesis of Chiral Phosphole Oxides via Desymmetric C–H Arylation of o-Bromoaryl Phosphine Oxides

Yan Lin, Wei-Yang Ma, Qiao-Ying Sun, Yu-Ming Cui*, Li-Wen Xu*
  • Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, P. R. of China   Email: ym_cui@hznu.edu.cn   Email: liwenxu@hznu.edu.cn
Supported by: National Natural Science Foundation of China Grant / Award numbers ‘51303043’, ‘21472031’, ‘21503060’
Supported by: Science and Technology Department of Zhejiang Province Grant / Award number ‘2015C31138’
Further Information

Publication History

Received: 08 February 2017

Accepted after revision: 05 March 2017

Publication Date:
11 April 2017 (eFirst)

Abstract

A palladium-catalyzed intramolecular direct arylation reaction of o-bromoaryl phosphine oxides was developed to afford a variety of P-stereogenic phosphole oxides in good yields. The enantioselectivities were closely associated with the specific structures of substrates, which ranged from 4–94%. As a result of ready availability of starting materials and simple operation to improve the enantioselectivities of the products with low ee values, the method provides a simple and straightforward procedure for the synthesis of P-stereogenic phosphole oxides.

Supporting Information

 
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    • 16a General Procedure for the Synthesis of o-Bromoarylphosphine Oxide To a stirred solution of o-bromoiodobenzene (1.3 mL, 10 mmol) in THF (10 mL) was added dropwise a solution of isopropylmagnesium chloride (2.0 M in THF, 5 mL, 10 mmol) at –40 °C. After 1 h, PCl3 (0.9 mL, 10 mmol) was added and stirred for 40 min at the same temperature. The mixture was then allowed to stand at r.t. for 12 h and cooled at –40 °C again. A solution of proper arylmagnesium bromide (1.0 M in THF, 22 mL, 22 mmol) was added dropwise. After 1 h, the resulting mixture was then stirred at r.t. overnight. A sat. aq solution of NH4Cl was added, and the reaction mixture was extracted three times with Et2O. The combined organic layer was washed with water and brine and dried over MgSO4. The solvent was then evaporated in vacuo, and the residue was purified by silica gel column chromatography with hexane as eluent to afford the corresponding phosphines. After oxidation by H2O2 in acetone, the crude products were purified by using flash chromatography with EtOAc as eluent, giving the pure products. Compound 1a: 1H NMR (400 MHz, CDCl3): δ = 7.67 (dddd, J = 12.9, 5.8, 4.8, 3.4 Hz, 2 H), 7.48–7.37 (m, 4 H), 7.31 (dd, J = 7.5, 4.3 Hz, 2 H), 7.26–7.14 (m, 4 H), 2.50 (s, 6 H). 31P NMR (202 MHz, CDCl3): δ = 35.37 (s). 13C NMR (101 MHz, CDCl3): δ = 143.45 (d, J = 7.9 Hz), 135.82 (d, J = 9.8 Hz), 134.89 (d, J = 7.4 Hz), 133.63 (t, J = 9.5 Hz), 133.14 (d, J = 2.2 Hz), 132.70 (s), 132.19–131.79 (m), 130.00 (s), 128.95 (s), 127.24 (d, J = 10.8 Hz), 126.88 (d, J = 4.4 Hz), 125.40 (d, J = 13.2 Hz), 21.92 (d, J = 4.1 Hz).
    • 17a General Procedure for the Synthesis of P-Stereogenic Phosphole Oxide To a mixture of ortho-bromoarylphosphine oxides 1al (1.0 mmol), Cs2CO3 (489 mg, 1.5 mmol), Pd(OAc)2 (11.2 mg, 5 mol%), and L4 (30.6 mg, 10 mol%) under nitrogen atmosphere was added 4 mL of xylene in a 25 mL Schlenk tube equipped with a magnetic stir bar. The Schlenk tube was stirred at r.t. for 20 min and then at 140 °C for 4 h. The reaction mixture was cooled to r.t. and quenched with water and then extracted with CH2Cl2. The extraction was washed with brine and dried over Na2SO4. The solvent was then evaporated in vacuo, and the residue was purified by using SiO2 column with EtOAc as eluent to afford the final products. Compound 2a: 1H NMR (400 MHz, CDCl3): δ = 8.20 (dd, J = 13.7, 7.6 Hz, 1 H), 7.72 (d, J = 7.7 Hz, 1 H), 7.57 (t, J = 8.6 Hz, 2 H), 7.48 (t, J = 7.6 Hz, 1 H), 7.43–7.32 (m, 2 H), 7.29 (t, J = 7.5 Hz, 2 H), 7.04 (dd, J = 12.1, 6.0 Hz, 2 H), 2.25 (s, 3 H), 1.79 (s, 3 H). 31P NMR (202 MHz, CDCl3): δ = 31.93 (s). 13C NMR (101 MHz, CDCl3): δ = 142.53 (s), 142.26 (d, J = 10.5 Hz), 142.11 – 141.87 (m), 141.02 (d, J = 11.0 Hz), 134.31 (d, J = 9.5 Hz), 133.55 (d, J = 7.9 Hz), 133.14 (d, J = 2.0 Hz), 132.54 (s), 132.23 (d, J = 2.7 Hz), 131.40 (t, J = 11.3 Hz), 130.83 (d, J = 9.8 Hz), 130.24 (s), 129.33 (t, J = 11.0 Hz), 128.72 (s), 127.74 (s), 126.01 (d, J = 11.9 Hz), 121.31 (d, J = 10.0 Hz), 118.75 (d, J = 10.1 Hz), 20.10 (d, J = 4.4 Hz), 19.42 (d, J = 4.6 Hz). Enantiomeric excess was determined by HPLC with a Chiralpak OD column (hexanes–2-PrOH = 70:30, 0.5 mL/min, 254 nm); major enantiomer t R = 12.3 min, minor enantiomer t R = 25.9 min. ESI-HRMS: m/z: [M + H]+ calcd for C20H17OP: 305.1090; found: 305.1094. [α]D 20 –36.2 (c 1.21, CHCl3).
  • 18 CCDC 1524935 (2a) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.