Transition metal complex, chiral α-amino tertiary borate and preparation method thereof
A technology of amino tri-boronate, which is applied in the field of transition metal complexes and can solve problems such as the lack of very efficient synthesis methods
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Embodiment 1
[0072] {(norbornadiene)[(R)-3-(tert-butyl)-4-(2,6-dimethoxyphenyl)-2,3-dihydrobenzo[d][1,3] Phosphine oxide-penta-yoke} rhodium tetrafluoroborate, namely [Rh(nbd)((R)-BIDIME)]BF 4 preparation of
[0073]
[0074] Under the protection of nitrogen, bis(norbornadiene) rhodium (I) tetrafluoroborate (198 mg, 0.53 mmol, 1.0 equiv) was dissolved in tetrahydrofuran (2 mL), and the ligand (R)- 3-(tert-butyl)-4-(2,6-dimethoxyphenyl)-2,3-dihydrobenzo[d][1,3]phosphine-pentyl conjugate (A, 182mg, 0.55mmol , 1.04equiv) in tetrahydrofuran (1mL) solution. After the reaction system was stirred at room temperature for 0.5 hours, the vacuum pump concentrated under reduced pressure to remove most of the solvent, added degassed ether (1 mL), stirred for 10 minutes, and filtered under nitrogen to obtain a red solid as the target {(norbornadiene)[ (R)-3-(tert-butyl)-4-(2,6-dimethoxyphenyl)-2,3-dihydrobenzo[d][1,3]phosphine oxide-pentanylated}tetrafluoro Rhodium borate, [Rh(nbd)((R)-BIDIME)]BF...
Embodiment 2
[0077]
[0078] Oxime Synthesis:
[0079] Dissolve the corresponding aryl ketone (100mmol, 1equiv) in a mixed solvent of ethanol and water (250mL, v / v=1 / 1), add hydroxylamine hydrochloride (200mmol, 2equiv) and anhydrous sodium acetate (400mmol, 4equiv) . Stir at room temperature. The reaction was monitored by TLC. After the reaction was completed, the ethanol was removed by a rotary evaporator to precipitate a solid, which was washed with water to obtain the corresponding oxime. Purification by column chromatography can be carried out as required, and the yield is 81-93%.
[0080] Preparation of enamides:
[0081] Under nitrogen protection, the prepared corresponding oxime (4mmol, 1equiv, 0.2M) was dissolved in 20mL THF, and acetic acid (12mmol, 3equiv) and acetic anhydride (8mmol, 2equiv) were added. With vigorous stirring, ferrous acetate (8 mmol, 2 equiv) was added. Heat to raise the temperature, and stir at reflux for 5 to 12 hours. The reaction was monitored by...
Embodiment 3
[0124]
[0125] First, methylmagnesium chloride (16.5mmol, 3.0M in THF, 5.5mL) was added into 50mL THF solution for dilution. Benzonitrile (15 mmol) dissolved in 20 mL THF was added dropwise to the vigorously stirred tetrahydrofuran solution of methylmagnesium chloride at 0°C. After the tetrahydrofuran solution of benzonitrile was added dropwise, the reaction solution was stirred at 0°C for half an hour, and then the solution was heated and refluxed for about 6 hours. The reaction was monitored by TLC. Thereafter, the temperature of the reaction solution was lowered to 0°C. With vigorous stirring, ethyl benzoate (18 mmol) dissolved in THF (20 mL) was added slowly. Heating to reflux for about 8h. Sufficient MeOH was added to obtain a homogeneous solution, then a mixture of water and ethyl acetate (volume ratio 1:1, 100 mL) was added, the organic phase was separated and the aqueous phase was extracted three times (50 mL) with ethyl acetate. The organic phases were combine...
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