CN106831508A - A kind of method for being catalyzed asymmetric oxidation thioether - Google Patents
A kind of method for being catalyzed asymmetric oxidation thioether Download PDFInfo
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- CN106831508A CN106831508A CN201510881333.4A CN201510881333A CN106831508A CN 106831508 A CN106831508 A CN 106831508A CN 201510881333 A CN201510881333 A CN 201510881333A CN 106831508 A CN106831508 A CN 106831508A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
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Abstract
The present invention provides a kind of asymmetric oxidation method of thioether.The chiral complex for using four tooth nitrogen organic ligands and metal scadium compound to be formed is catalyst, with hydrogen peroxide as oxidant, asymmetry catalysis oxidation reaction is carried out to such thioether, corresponding chiral sulfoxides are obtained, its yield enantioselectivity is all higher than 90%.The reaction has cleaning, and reaction condition is gentle, high conversion and corresponding selection.With industrial prospect.
Description
Technical field
The present invention relates to the method that the asymmetric oxidation to thioether prepares chiral sulfoxide.
Background technology
Chiral sulfoxide is a kind of important organic synthesis intermediate, in essences such as medicine, spices, food additives
Have in the synthesis of thin chemicals and be extremely widely applied.Therefore, the preparation of chiral sulfoxide has important reason
By and realistic meaning.The current transition metal-catalyzed thioether asymmetric oxidation system of document report is by chiral ligand point
Class mainly includes chiral diol (phenol)-titanium catalyst system, chiral three hydramine-titanium, chirality porphyrin metal complex
Catalyst system and catalyzing, chiral Salen metal complexs catalyst system and catalyzing and Chiral Schiff Base metal complex are catalyzed
System (Arkivoc, 2011, (i), 1-110；Journal of Sulfur Chemistry,2013,34(3),
301-341)。
Although above-mentioned system can realize the asymmetric oxidation reaction of thioether, catalyst amount is still suffered from greatly,
The problems such as substrate narrow application range, not environment friendly and reaction time long.These problems all limit thioether
The industrial production of asymmetric oxidation reaction.
The content of the invention
It is an object of the invention to provide a kind of efficient, highly-solid selectively, quickly, environment-friendly catalysis
The new method of thioether asymmetric oxidation reaction synthesis of chiral sulfoxide.
To reach above-mentioned purpose, the technical solution adopted by the present invention：
A kind of method that chiral sulfoxides are prepared for asymmetry catalysis sulfide oxidation, in organic solvent,
It is oxidant with hydrogen peroxide, is with the complex compound that chiral four teeth nitrogen organic ligand and metal scadium compound are formed
Catalyst, is chiral sulfoxide by sulfide oxidation.Wherein, chiral ligand and the mol ratio of scadium compound are 1:1,
Chiral ligand is 1 with the mol ratio of substrate:5000~1:50, preferably 1:1000~1:100.Hydrogen peroxide and bottom
The mol ratio of thing is 1:1~10:1, preferably 1.5:1~2.5:1.
The thioether is R4-S-R5, and wherein R4, R5 is respectively selected from the aryl of C6-12, the aryl of C6-12
(aryl methyl of C6-12 aryl and C6-12 can not replace base or with halogen, C1-4 to methyl
Alkyl, C1-4 alkoxies, the alkoxy carbonyl of C2-5, nitro or-CN substitutions base), C1-6 alkyl (C1-6
Alkyl can not replaced base or contain halogen, nitro, and hydroxyl or-CN replace base.
Corresponding chiral sulfoxide compound isWherein R4, R5It is respectively selected from C6-12Aryl, C6-12Virtue
Ylmethyl (C6-12Aryl and C6-12Aryl methyl can not replace base or with halogen, C1-4Alkane
Base, C1-4Alkoxy, C2-5Alkoxy carbonyl, nitro or-CN substitution base), C1-6Alkyl (C1-6Alkyl can
To be not replace base or contain halogen, nitro, hydroxyl or-CN substitution bases.
Manganese compound of the present invention is TFMS manganese [Sc (OTf)3]。
Chiral four teeth nitrogen ligand of the present invention is the compound with following structure, wherein R1, R2, R3
Respectively hydrogen, alkyl (molecular formula is CnH2n+1, n=1-5), aryl, (molecular formula is aryl alkyl
C6H5CnH2n+1, n=1-5) or alkoxy (molecular formula is OCnH2n+1, n=1-5), R1, R2, R3
It is identical or different；X is O, S or N.
Organic solvent organic solvent of the present invention is acetonitrile, methyl alcohol, in tetrahydrofuran or dichloromethane one
Plant, preferably tetrahydrofuran.The mass concentration of hydrogen peroxide is 15wt%~70wt%, preferably 30wt%~50
Wt%.Reaction temperature is -70 DEG C~20 DEG C, preferably -30 DEG C~0 DEG C.Reaction time 5-30min.
Yield enantioselectivity of the present invention is all higher than 90%.The reaction has cleaning, and reaction condition is gentle, high
Conversion ratio and enantioselectivity.With industrial prospect.
Due to the utilization of above-mentioned technology, the present invention has following advantages compared with prior art：
1. metallic compound is cheap and easy to get；
2. reaction speed is fast；
3. additive-free
4. part is recyclable after reacting, and reuses；
Specific embodiment
Embodiment 1
The investigation of reaction condition
Under the conditions of 25 DEG C, Sc (OTf) 3 (1.0mg, 0.0021mmol) is added in 1.0mL THF
4h is stirred with L2 (1.0mg, 0.0021mmol).Reactant mixture is cooled to 0 DEG C, Ran Houjia
Enter 0.42mmol thioethers and 45% hydrogen peroxide (0.42mmol), 1h is stirred at maintaining 0 DEG C.
Ethyl acetate is extracted, the washing of 10% hypo solution, merges organic phase, is dried, high performance liquid chromatography
Analysis obtains ee values, and column chromatography obtains product, is calculated yield.
Reaction condition is optimized by model substrates of phenyl methyl sulfide.Result such as following table.
A separation yields.B chiral high performance liquid chromatographies are detected.
From table, solvent is tetrahydrofuran, and hydrogen peroxide is 1.5 with the mol ratio of substrate thioether：1, instead
Preferably, the reaction result of the chiral four teeth nitrogen ligand of different structure is different, L2 for result when to answer temperature be -20 DEG C
Result be better than other parts.
8.3),6.40(1H,d,J 9.8),5.66(1H,d,J 9.8),1.48(3H,s)；13C NMR(100MHz,CDCl3)
δ153.17(s),141.47(s),134.46(s),131.68(s),129.29(s),127.24(s),125.58
(s),122.93(s),122.01(s),117.20(s),77.50(dd,J 62.4,30.4),28.71(s)；ee
Value measures (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios),
Flow velocity:0.5mL/min, wavelength：254nm.).
2 chiral ligand L2-Sc (OTf) of embodiment 3 is catalyzed thioether asymmetric oxidation reaction
The characterize data of portion of product is as follows：
8.3),6.40(1H,d,J 9.8),5.66(1H,d,J 9.8),1.48(3H,s)；13C NMR(100MHz,CDCl3)
δ153.17(s),141.47(s),134.46(s),131.68(s),129.29(s),127.24(s),125.58
(s),122.93(s),122.01(s),117.20(s),77.50(dd,J 62.4,30.4),28.71(s)；ee
Value measures (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios),
Flow velocity:0.5mL/min, wavelength：254nm.).
(s,3H)；13C NMR(100MHz,CDCl3)δ13C NMR(101MHz,CDCl3)δ144.38(s),
132.54(s),130.34(s),128.73(s),125.88(s),42.22(s)；Ee values are surveyed by Chiral HPLC
Obtain (chromatographic column：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios), flow velocity:0.5mL/min,
Wavelength：254nm.).
Mutually measure (chromatographic column：DAICEL OD-H, mobile phase：N-hexane/isopropanol=95:5 (volume ratios), flow velocity:0.5mL/min,
Wavelength：254nm.).
144.85(s),137.80(s),130.21(s),125.54(s),44.61(s)；Ee values are by hand
Property efficient liquid phase measures (chromatographic column：DAICEL OD-H, mobile phase：N-hexane/isopropanol=95:5 (volume ratios), flow velocity:
0.5mL/min, wavelength：220nm.).
(101MHz,CDCl3)δ133.50(s),132.83(s),129.32(s),126.28(s),119.00(s),42.49
(s)；Ee values measure (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (bodies
Product ratio), flow velocity:0.5mL/min, wavelength：220nm.).
Value measures (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios),
Flow velocity:0.5mL/min, wavelength：220nm.).
126.01(s),125.72(s),77.96(s),77.65(s),77.33(s),44.57(s)；Ee values are by chirality
Efficient liquid phase measures (chromatographic column：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios), flow velocity:0.5
ML/min, wavelength：220nm.).
(d, J=8.8Hz), 117.35 (s), 117.13 (s), 77.98 (s), 77.67 (s), 77.35 (s), 44.70 (s)；
Ee values measure (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volumes
Than), flow velocity:0.5mL/min, wavelength：220nm.).
δ 153.87 (s), 125.15 (d, J=19.5Hz), 44.45 (s)；Ee values are by chiral high performance liquid
Mutually measure (chromatographic column：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios), flow velocity:0.5mL/min,
Wavelength：254nm.).
142.09(s),130.59(s),124.10(s),44.49(s),21.93(s)；Ee values are surveyed by Chiral HPLC
Obtain (chromatographic column：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios), flow velocity:0.5mL/min,
Wavelength：220nm.)..
MHz,CDCl3)δ162.53(s),137.13(s),135.17–133.68(m),126.02(s),
115.42(s),78.01(s),77.69(s),77.38(s),56.09(s),44.53(s)；Ee values are by chiral high
Effect liquid phase measures (chromatographic column：DAICEL OD-H, mobile phase：N-hexane/isopropanol=70:30 (volume ratios), flow velocity:0.5
ML/min, wavelength：220nm.).
δ145.80(s),144.18(s),128.16(s),124.20(s),64.57(s),44.22；
Ee values measure (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol=70:30 (volumes
Than), flow velocity:0.5mL/min, wavelength：220nm.).
1H),1.04–0.96(m,1H),0.95–0.87(m,2H)；13C NMR(100MHz,CDCl3)
δ145.49(s),134.06(s),131.48(s),129.72(s),128.11(s),124.58(s),34.37
(s),3.97(s),3.32(s)；Ee values measure (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：
N-hexane/isopropanol=90:10 (volume ratios), flow velocity:0.5mL/min, wavelength：220nm.).
White solid, silica gel column chromatography separates (ethyl acetate：N-hexane=20：80 (volume ratios)) (86%)1H
125.55(s),77.96(s),77.64(s),77.32(s),55.10(s),16.43(s),14.48(s).ee
Value measures (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios),
Flow velocity:0.5mL/min, wavelength：220nm.).
142.23(s),139.63(s),132.34(s),129.21(s),125.76(s),122.73(s),77.97(s),
77.65 (s), 77.33 (s), 55.06 (s), 21.98 (s), 16.53 (s), 14.52 (s) .ee values are by chiral high
Effect liquid phase measures (chromatographic column：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios), flow velocity:0.5
ML/min, wavelength：220nm.).
(d, J=6.8Hz, 3H)；13C NMR(101MHz,CDCl3)δ141.94(s),138.99(s),
130.13(s),125.58(s),78.00(s),77.68(s),77.36(s),55.05(s),21.95(s),16.28
S (), 14.63 (s) .ee values measure (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/different
Propyl alcohol=90:10 (volume ratios), flow velocity:0.5mL/min, wavelength：220nm.).
1H), 1.13 (t, J=7.4Hz, 3H)；13C NMR(100MHz,CDCl3)δ143.80(s),131.49(s),
129.69(s),124.72(s),78.01(s),77.70(s),77.38(s),50.81(s),6.50(s)；ee
Value measures (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios),
Flow velocity:0.5mL/min, wavelength：220nm.).
- 3.48 (m, 1H), 3.29 (s, 3H), 2.90 (t, J=5.6Hz, 2H)；13C NMR(100MHz,CDCl3)
δ144.53(s),131.62(s),129.84(s),124.45(s),65.83(s),59.53(s),58.71(s).
Ee values measure (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol=70:30 (volumes
Than), flow velocity:0.5mL/min, wavelength：220nm.).
3.96-3.84 (m, 1H), 3.05 (ddd, J=13.5,8.9,4.6Hz, 1H), 2.96-2.86 (m, 1H)；13C NMR(100MHz,CDCl3)δ143.61(s),131.79(s),129.99(s),124.56(s),77.39
(s),60.05(s),56.81(s)；Ee values measure (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：
N-hexane/isopropanol=90:10 (volume ratios), flow velocity:1.0mL/min, wavelength：220nm.).
3.98 (d, J=12.6Hz, 1H)；13C NMR(100MHz,CDCl3)13C NMR(101MHz,
CDCl3)δ131.72(s),130.93(s),129.42(s),129.03(s),128.81(s),125.02(s),
64.20(s)；Ee values measure (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol
=90:10 (volume ratios), flow velocity:1.0mL/min, wavelength：220nm.).
7.22 (dt, J=15.8,4.2Hz, 3H), 7.15-7.05 (m, 1H), 7.00-6.90
(m, 2H), 4.07 (d, J=12.5Hz, 1H), 3.98 (d, J=12.5Hz, 1H), 2.05 (s, 3H)；13C
NMR(101MHz,CDCl3) δ 136.13 (s), 131.45 (s), 130.83 (d, J=19.1Hz), 129.02 (s),
128.81 (s), 127.65 (s), 124.79 (s), 62.92 (s), 18.55 (s) .ee values are surveyed by Chiral HPLC
Obtain (chromatographic column：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios), flow velocity:1.0mL/min,
Wavelength：220nm.).
1H),2.32(s,3H)；13C NMR(100MHz,CDCl3)δ139.64(s),132.52(s),130.96(s),
129.21 (s), 128.89 (d, J=19.0Hz), 125.31 (s), 122.11 (s), 64.28 (s), 21.86 (s)；
Ee values measure (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volumes
Than), flow velocity:1.0mL/min, wavelength：220nm.).
3.95 (d, J=12.5Hz, 1H), 2.38 (s, 3H)；13C NMR(100MHz,CDCl3)δ130.94(s),130.13
(s), 129.12 (d, J=20.0Hz), 128.75 (s), 125.05 (s), 64.32 (s), 22.02 (s)；ee
Value measures (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios),
Flow velocity:1.0mL/min, wavelength：220nm.).
1.72-1.47 (m, 2H), 1.37 (ddt, J=13.8,8.9,7.1Hz, 2H), 0.85 (t, J=7.3Hz,
3H)；13C NMR(100MHz,CDCl3)δ150.19(s),131.83(s),131.62(s),127.62(s),123.19
(s),122.93(s),121.76(s),119.44(s),117.04(s),36.36(s),25.88(s),24.82
S (), 21.90 (s) .ee values measure (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：N-hexane/different
Propyl alcohol=90:10 (volume ratios), flow velocity:1.0mL/min, wavelength：220nm.).
2H), 1.42-1.11 (m, 4H), 0.80 (t, J=7.1Hz, 3H)；13C NMR(100
MHz,CDCl3)13C NMR(100MHz,CDCl3)δ141.86(s),141.35(s),130.41(s),124.59
(s),78.05(s),77.73(s),77.41(s),57.90(s),31.33(s),22.78(s),22.42(s),
21.91(s),14.33(s)；Ee values measure (chromatographic column by Chiral HPLC：DAICEL OD-H, mobile phase：Just oneself
Alkane/isopropanol=70:30 (volume ratios), flow velocity:0.5mL/min, wavelength：220nm.).
(dd, J=5.2,1.6Hz, 3H)；13C NMR(100MHz,CDCl3)δ145.74(s),144.49(s),135.98
(s), 135.14 (s), 132.09 (d, J=12.2Hz), 129.78 (d, J=18.3Hz), 128.83 (s), 127.37
(s), 126.91 (s), 125.92 (s), 77.94 (s), 77.62 (s), 77.30 (s) .ee values are by chiral high performance liquid
Mutually measure (chromatographic column：DAICEL OD-H, mobile phase：N-hexane/isopropanol=90:10 (volume ratios), flow velocity:1.0mL/min,
Wavelength：220nm.).
Claims (10)
1. it is a kind of be catalyzed asymmetric oxidation thioether method, it is characterised in that：
In organic solvent, it is oxidant with hydrogen peroxide, with chiral four teeth nitrogen organic ligand and metal scandium
The complex compound that compound is formed is catalyst, and substrate pro-chiral sulphide is oxidized to the sulfoxide compound of chirality；
Wherein, chiral four teeth nitrogen organic ligand and the mol ratio of scadium compound are 1:1, chiral four teeth nitrogen is organic to match somebody with somebody
Body is 1 with the mol ratio of substrate thioether:5000~1:50；Hydrogen peroxide is with the mol ratio of substrate thioether
1:1~10:1.
2. in accordance with the method for claim 1, it is characterised in that：
Chiral four tooth nitrogen organic ligands are preferably 1 with the mol ratio of substrate thioether:1000~1:100；Peroxidating
Hydrogen is preferably 1.5 with the mol ratio of substrate thioether:1~2.5:1.
3. in accordance with the method for claim 1, it is characterised in that：The oxidant was used
Oxidation aqueous solution of hydrogen, the mass concentration of hydrogen peroxide is 15wt%~70wt%；The quality of hydrogen peroxide is dense
Degree is preferably 30wt%~50wt%.
4. in accordance with the method for claim 1, it is characterised in that：Reaction temperature is -70 DEG C~20 DEG C；
Reaction temperature is preferably -30 DEG C~0 DEG C.
5. in accordance with the method for claim 1, it is characterised in that：Scadium compound is fluoroform sulphur
Sour scandium [Sc (OTf) 3].
6. in accordance with the method for claim 1, it is characterised in that：Chiral four tooth nitrogen organic ligands can
Recycle.
7. in accordance with the method for claim 1, it is characterised in that：Described chiral four teeth nitrogen ligand
The compound with following structure, wherein R1, R2, R3 be respectively hydrogen, alkyl (molecular formula is CnH2n+1,
N=1-5), aryl, aryl alkyl (molecular formula is C6H5CnH2n, n=1-5) or alkoxy (molecular formula
It is OCnH2n+1, n=1-5), R1, R2, R3 are identical or different；X is O, S or N；
8. in accordance with the method for claim 1, it is characterised in that：
The thioether is R4-S-R5, and wherein R4, R5 is respectively selected from the aryl of C6-12, or C6-12 virtues
Halogen, C1-4 alkyl, C1-4 alkoxies, the alkoxy carbonyl of C2-5, nitro or-CN are carried on base
The substituted aryl of one or two or more kinds in substitution base, aryl alkyl (molecular formula is C6H5CnH2n,
N=1-5 halogen, C1-4 alkane), or on aryl alkyl (molecular formula is C6H5CnH2n, n=1-5) are carried
In base, C1-4 alkoxies, the alkoxy carbonyl of C2-5, nitro or-CN substitution base it is a kind of or two kinds with
On substituted aryl alkyl, on C1-6 alkyl, or C1-6 alkyl contain halogen, nitro, hydroxyl or-CN
The substitution alkyl of one or two or more kinds in substitution base.
9. according to the method described in claim 1 or 8, it is characterised in that：
Corresponding chiral sulfoxide compound isWherein R4, R5It is respectively selected from C6-12Aryl, or
C6-12Halogen, C are carried on aryl1-4Alkyl, C1-4Alkoxy, C2-5Alkoxy carbonyl, nitro or-CN
The substituted aryl of one or two or more kinds in substitution base, (molecular formula is C to aryl alkyl6H5CnH2n, n=1-5),
Or aryl alkyl (molecular formula is C6H5CnH2n, n=1-5) and carry halogen, C1-4Alkyl, C1-4Alkoxy,
C2-5Alkoxy carbonyl, nitro or-CN substitution base in the substituted aryl methyl of one or two or more kinds, C1-6
Alkyl, or C1-6On alkyl containing halogen, nitro, hydroxyl or-CN substitution base in one or two or more kinds
Substitution alkyl.
10. according to the method described in claim 1 or 8, it is characterised in that：
Organic solvent is acetonitrile, methyl alcohol, the preferably one kind in tetrahydrofuran or dichloromethane, tetrahydrofuran.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754604A (en) * | 2020-06-05 | 2021-12-07 | 江苏奥赛康药业有限公司 | Nitrogen-containing chiral ligand and application thereof in asymmetric oxidation reaction of thioether |
| CN113754605A (en) * | 2020-06-05 | 2021-12-07 | 江苏奥赛康药业有限公司 | Nitrogen-containing ligand and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754604A (en) * | 2020-06-05 | 2021-12-07 | 江苏奥赛康药业有限公司 | Nitrogen-containing chiral ligand and application thereof in asymmetric oxidation reaction of thioether |
| CN113754605A (en) * | 2020-06-05 | 2021-12-07 | 江苏奥赛康药业有限公司 | Nitrogen-containing ligand and preparation method and application thereof |
| CN113754604B (en) * | 2020-06-05 | 2023-09-08 | 江苏奥赛康药业有限公司 | Nitrogen-containing chiral ligand and application thereof in asymmetric oxidation reaction of thioether |
| CN113754605B (en) * | 2020-06-05 | 2023-10-03 | 江苏奥赛康药业有限公司 | Nitrogen-containing ligand, and preparation method and application thereof |
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