Iridium catalyzed enantiotropic hydrosubstituting process of aromatic pyridine ring and pyrazine ring
An aromatic pyridine ring, enantioselective technology, applied in chemical instruments and methods, organic chemical methods, physical/chemical process catalysts, etc., can solve the problems of severe reaction conditions, destruction of aromaticity, unfavorable energy, etc. Gentle, easy-to-prepare effect
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Embodiment 1
[0033] Embodiment 1: optimization of conditions
[0034] Add [Ir(COD)Cl] to a reaction flask 2 (3.4 mg, 0.005 mmol) and the chiral ligand (0.011 mmol) and five mL of solvent. The reaction mixture was stirred under nitrogen for 30 minutes. Then transfer to the reaction kettle with substrate (1.0mmol) and adduct iodine (12.7mg, 0.05mmol) in advance, and pass through hydrogen (30-50atm) to react for 12 hours. Release hydrogen slowly, remove toluene and obtain pure product directly by column chromatography, the reaction formula is as follows:
[0035] The enantiomeric excess of the product can be determined by chiral HPLC, see Table 1.
[0036] Table 1: Asymmetric hydrogenation of 2-methylquinoline No. H 2 (psi); T solvent conversion ee(%)1 700; 25℃ CH 2 Cl 2 >99 852 700 25°C (ClCH 2 ) 2 >99 853 700; 25℃ MeOH 85 94 700; 25℃ i-PrOH >99 845 700; 25℃ THF >99 856 700; 25℃ Toluene >99 947 700; 25℃ Benzene >99 948 1500; 25℃ Toluene > 99 919 100; 25℃ Toluene 68 9410 700;...
Embodiment 2
[0037] Embodiment 2, the reaction of replacing quinoline substrate in addition
[0038] Add [Ir(COD)Cl] to a reaction flask 2 (3.4 mg, 0.005 mmol) and (R)-MeO-Biphep (6.4 mg, 0.011 mmol) and five mL of toluene. The reaction mixture was stirred under nitrogen for 30 minutes. Then transfer to the reaction kettle with substrate (1.0mmol) and adduct iodine (12.7mg, 0.05mmol) in advance, and pass through hydrogen (30-50atm) to react for 12 hours. Release hydrogen slowly, remove toluene and obtain pure product directly by column chromatography, the reaction formula is as follows: The enantiomeric excess of the product can be determined by chiral HPLC, see Table 2. Table 2. Asymmetric hydrogenation of substituted quinolines No. R' / R of 1 Yield Ee (absolute configuration) 1 H / Me(1a) 94(2a) 94(R)2 H / Et(1b) 88(2b ) 96(R)3 H / n-Pr(1c) 92(2c) 93(R)4 H / n-Bu(1d) 86(2d) 92(R)5 H / 3-Butenyl(1e) 91( 2d) e 92(R)6 H / n-Pentyl(1f) 92(2f) 94(R)7 H / Phenethyl(1g) 94(2g) 93(R)8 88(2h) 94(R)...
Embodiment 3
[0038] Add [Ir(COD)Cl] to a reaction flask 2 (3.4 mg, 0.005 mmol) and (R)-MeO-Biphep (6.4 mg, 0.011 mmol) and five mL of toluene. The reaction mixture was stirred under nitrogen for 30 minutes. Then transfer to the reaction kettle with substrate (1.0mmol) and adduct iodine (12.7mg, 0.05mmol) in advance, and pass through hydrogen (30-50atm) to react for 12 hours. Release hydrogen slowly, remove toluene and obtain pure product directly by column chromatography, the reaction formula is as follows: The enantiomeric excess of the product can be determined by chiral HPLC, see Table 2. Table 2. Asymmetric hydrogenation of substituted quinolines No. R' / R of 1 Yield Ee (absolute configuration) 1 H / Me(1a) 94(2a) 94(R)2 H / Et(1b) 88(2b ) 96(R)3 H / n-Pr(1c) 92(2c) 93(R)4 H / n-Bu(1d) 86(2d) 92(R)5 H / 3-Butenyl(1e) 91( 2d) e 92(R)6 H / n-Pentyl(1f) 92(2f) 94(R)7 H / Phenethyl(1g) 94(2g) 93(R)8 88(2h) 94(R)9 86(2i) 96(R)10 F / Me(1j) 88(2j) 96(R)11 Me / Me(1k) 91(2k) 91(R)12 MeO / Me(1l) 8...
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