Oxaspirophosphine-oxazoline ligand and preparation method and application thereof
An oxaspiro and oxazoline technology is applied in the field of oxaspirophosphine-oxazoline ligands and their preparation, and can solve the problems of long reaction steps, low product ee value, low total yield and the like
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[0037] A second aspect of the present invention provides a method for preparing an oxaspirophosphine-oxazoline ligand, which comprises the following steps,
[0038] (i) the compound represented by the formula (1) is prepared in a CO atmosphere under the action of a metal catalyst, a ligand and a base to obtain the compound represented by the formula (2),
[0039] (ii) the compound represented by the formula (2) and the compound represented by the formula (7) are subjected to a cyclization reaction to obtain the oxaspirophosphine-oxazoline ligand represented by the formula (3),
[0040]
[0041] In an embodiment of the method for preparing an oxaspirophosphine-oxazoline ligand of the present invention, in the step (1), the metal catalyst is palladium acetate.
[0042] In another embodiment of the method for preparing an oxaspirophosphine-oxazoline ligand of the present invention, in the step (1), the ligand is 1,3-bis(diphenylphosphino)propane.
[0043] In another embodimen...
Embodiment 1
[0084] Example 1 compound (S a )-2b preparation
[0085]
[0086] In an argon atmosphere, compound (S a )-1b (3.90 g, 7.0 mmol), methanol (42 mL), palladium acetate (259 mg, 1.16 mmol), dppp (478 mg, 1.46 mmol), dimethylsulfoxide (60 mL) and triethylamine (11.6 mL). The reaction mixture was reacted under a carbon monoxide atmosphere at 70°C until the reaction was complete. It was cooled to room temperature, extracted with ethyl acetate three times, and then the solvent in the mixture was removed under reduced pressure, and the crude product was directly hydrolyzed in the presence of potassium hydroxide. Finally, the compound (S) can be obtained by column chromatography a )-2b (2.02 g, yield 64%);
[0087] [α] 25 D =-32.00(c=0.5,acetone);
[0088] 1 H NMR (400MHz, Chloroform-d): δ 7.36-7.17 (m, 4H), 7.17-7.00 (m, 2H), 6.94 (d, J=6.5Hz, 1H), 6.76 (t, J=8.5Hz) , 4H), 6.54(s, 1H), 4.98(d, J=8.4Hz, 1H), 4.74(d, J=8.3Hz, 2H), 4.62(d, J=8.5Hz, 1H), 1.15(s , 18H), 1.13(...
Embodiment 2
[0090] Example 2 compound (R a )-2a preparation
[0091]
[0092] According to the method described in Example 1, compound (R a )-1a was prepared to obtain compound (R a )-2a, whose detection data is as follows:
[0093] [α] 25 D =+23.40(c=0.5, methanol);
[0094] 1 H NMR (400MHz, Chloroform-d): δ 7.32-7.22 (m, 4H), 7.22-7.14 (m, 3H), 7.13-7.01 (m, 4H), 6.90-6.79 (m, 2H), 6.67 ( m, 1H), 6.29 (dd, J=7.9, 0.8Hz, 1H), 5.73 (dd, J=8.0, 0.8Hz, 1H), 5.01 (dd, J=9.2, 2.6Hz, 1H), 4.67 (d , J=9.3Hz, 1H), 4.62 (dd, J=9.2, 1.3Hz, 1H), 4.53 (d, J=9.4Hz, 1H). 13 C NMR (101MHz, Chloroform-d): δ 161.29, 161.27, 160.25, 160.2, 143.5, 137.1, 137.0, 135.9, 135.7, 135.1, 135.0, 134.1, 133.9, 133.3, 133.1, 132.5, 1299.2, 130 128.7, 128.29, 128.25, 128.2, 128.1, 128.0, 127.8, 127.7, 110.9, 108.8, 83.3, 80.7, 56.1. 31 P NMR (162MHz, Chloroform-d): δ-22.55;
[0095] HRMS(ESI)calcd.for C 28 H 20 O 4 P[M-H] - :451.1105.Found:451.1104.
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