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Chiral azaspirene salt compound and preparation method thereof

A salt compound and compound technology are applied in the field of chiral azaspiroene salt compounds and their preparation, and can solve problems such as failure to successfully prepare chiral azaspiroene salt compounds and the like

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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] The technical problem to be solved by the present invention is that the prior art cannot successfully prepare chiral azahelicene salt compounds. Therefore, the present invention provides a class of chiral Azahelicene salt compound and preparation method thereof, the preparation method can synthesize chiral azahelicene salt compound in one step, has excellent yield and enantioselectivity, and has good substrate universality

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  • Chiral azaspirene salt compound and preparation method thereof
  • Chiral azaspirene salt compound and preparation method thereof
  • Chiral azaspirene salt compound and preparation method thereof

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Experimental program
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Embodiment 1

[0175] Embodiment 1 Synthesis of compound shown in formula I

[0176]

[0177] Under argon atmosphere, [SCpRh] (2.6mg, 0.005mmol), A2 (6.8mg, 0.02mmol), AgF (38.0mg, 0.30mmol), NaOTf (34.4mg, 0.20mmol), Compound II (0.10mmol) and the corresponding alkyne III (0.10mmol, 1.0equiv.), MeOH (1.0mL) and water (18mg, 1.0mmol) were then heated to 80°C for reaction. After the reaction, dilute with dichloromethane, filter with neutral alumina, remove the solvent residue under reduced pressure and separate by neutral alumina column chromatography to obtain the target product I (methanol / dichloromethane=1 / 20).

Embodiment 2

[0178] The synthesis of embodiment 2 compound I-1

[0179]

[0180] (62.5 mg, 99% yield, 91% ee). Analytical data: 1 H NMR (400MHz, CD 2 Cl 2 )δ8.62(d, J=7.1Hz, 1H), 8.50(d, J=8.5Hz, 1H), 8.35(d, J=8.8Hz, 1H), 8.22(d, J=7.1Hz, 1H) ,8.14(d,J=8.6Hz,1H),8.05(d,J=7.8Hz,1H),8.01(d,J=7.9Hz,1H),7.70(d,J=8.9Hz,1H),7.57 –7.29(m,13H),7.00–6.91(m,2H). 13 C NMR (101MHz, CD 2 Cl 2 )δ141.5,140.4,137.7,137.2,135.7,135.1,135.0,133.9,133.4,132.8,131.3,131.0,130.8,130.7,130.6,130.1,129.8,129.7,129.4,129.1,129.1,128.9,128.8,128.8,128.7 ,128.6,128.6,128.5,128.0,127.7,125.8,125.7,124.3,124.0,123.7,122.6,122.3. 19 F NMR (377MHz, CD 2 Cl 2 )δ-78.99. Chiralpak IB N-3column, 0.46cmI.D.×25cm L×3μm, 0.2% propylamine (adjust pH=3 with phosphoric acid) a.q. / acetonitrile, 50:50v / v, flow rate 0.4mL / min , detection wavelength λ=254nm,t R (major)=63.46min,t R (minor) = 67.91min.

Embodiment 3

[0181] The synthesis of embodiment 3 compound 1-2

[0182]

[0183] (63.8 mg, 97% yield, 93% ee). Analytical data: 1 H NMR (400MHz, CD 2 Cl 2 )δ8.64(d, J=7.1Hz, 1H), 8.51(d, J=7.1Hz, 1H), 8.45(d, J=8.5Hz, 1H), 8.37(d, J=8.9Hz, 1H) ,8.25(d,J=8.6Hz,1H),8.09–7.94(m,2H),7.67(d,J=8.8Hz,1H),7.66–7.58(m,1H),7.56–7.43(m,4H ),7.41(d,J=8.6Hz,1H),7.38–7.30(m,2H),7.28–7.19(m,2H),7.18–7.08(m,2H),6.99–6.87(m,2H). 13 C NMR (101MHz, CD 2 Cl 2 )δ164.5 (d, J=104.1Hz), 162.0 (d, J=100.6Hz), 141.8, 139.8, 137.6, 137.2, 135.1, 135.0, 134.9, 133.9 (d, J=8.8Hz), 133.4, 133.2 (d, J=8.7Hz),132.9,132.8,132.3(d,J=8.4Hz),129.9(d,J=3.7Hz),129.4,129.0,129.0,128.8,128.8,128.6(d,J=9.4 Hz), 128.0, 127.7, 126.7(d, J=3.7Hz), 125.9, 125.9, 124.4, 124.1, 123.6, 122.6, 122.1, 117.3(d, J=22.2Hz), 117.0(d, J=22.2Hz) ,116.0(d,J=21.8Hz),115.7(d,J=22.1Hz). 19 F NMR (377MHz, CD 2 Cl 2 )δ-79.04, -108.69, -112.52. Chiralpak IB N-3column, 0.46cm I.D.×25cm L×3μm, 0.2% propylamine (phosphoric acid to adjust p...

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Abstract

The invention discloses a chiral azaspirene salt compound and a preparation method thereof. The invention provides a preparation method of a compound 1. The preparation method comprises the followingsteps: in a solvent, in the presence of a rhodium catalyst, an oxidant and a chiral acid, reacting a compound as shown in a formula II with a compound as shown in a formula III to obtain the compound1, wherein the compound 1 is a chiral azaspirene salt compound as shown in a formula I or a chiral azaspirene salt compound as shown in a formula I. The method can be used for synthesizing the chiralazaspirene salt compound in one step, has excellent yield and enantioselectivity, and is relatively good in substrate universality.

Description

technical field [0001] The invention relates to a chiral azahelicene salt compound and a preparation method thereof. Background technique [0002] Helicene is a class of polycyclic aromatic compounds with a helical structure formed by the fusion of multiple aromatic rings in the ortho position. Due to their unique structural characteristics, chiral helicene and its derivatives are widely used in the fields of chiral catalysts, chiral materials, chiral molecular recognition, biomedicine and other fields (Shen, Y.; Chen, C.-F. Chem .Rev.2012,112,1463; Gingras,M.,Chem.Soc.Rev.2013,42,968.;Gingras,M.;Félix,G.;Peresutti,R.,Chem.Soc.Rev.2013,42, 1007; Gingras, M., Chem.Soc.Rev.2013, 42, 1051; Dhbaibi, K.; Favereau, L.; Crassous, J., Chem.Rev.2019, 119, 8846; Zhao, W.-L .; Li, M.; Lu, H.-Y.; Chen, C.-F., Chem. Commun. 2019, 55, 13793; Chen, C.-F.; Chen, Y. Helicene Chemistry: From Synthesis to Applications; Springer: Berlin, 2017.). The catalytic asymmetric synthesis of chiral ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D455/03B01J31/22
CPCC07D455/03B01J31/2295B01J31/2291C07B2200/07B01J2531/822B01J2531/0225B01J2531/0238
Inventor 游书力王强张文文郑超顾庆
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