CN1446633A - Chirality catalyst for oxidative coupling naphthol - Google Patents
Chirality catalyst for oxidative coupling naphthol Download PDFInfo
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Abstract
A chiral catalyst for preparing binaphthalenol and its derivatives with high optical purity by catalytic oxidation and coupling of naphthalenol and its derivatives is the complex of vanadium and the Schiff base prepared from chiral amino acid and chiral formacylbinaphthalenol.
Description
The invention belongs to the organic chemistry asymmetric catalysis field, specifically is a kind of chiral catalyst that is used for oxidative coupling naphthol.
Optically pure binaphthol and derivative thereof extensively as chiral auxiliary and part, show very high three-dimensional control ability [Chem.Rev.1998,98,2405 in series reaction in asymmetric syntheses; Acc.Chem.Res.1990,23,345].Because this compounds is extremely important, encouraging people to seek the effective ways of synthetic this compounds in recent years always.Obtain optically pure binaphthol and mainly contain following method:
1. method for splitting
Earlier with catalyst naphthols is oxidized to the binaphthol of racemization, splits with inclusion or chemical method for splitting obtains optically pure binaphthol again, method for splitting is that what to obtain this compounds effectively also is topmost method.But split the resolution reagent that generally needs equivalent, resolution reagent generally all compares expensive, and, fractionation can only obtain maximum 50% yield, and the recovery of resolving agent also is a problem, these drawbacks limit its practical application [Bioorg.Chem.1978,7,7397; J.Org.Chem.1998,53,3607; Tetrahedron Lett.1987,28,355; J.Org.Chem.1981,46,4988; Tetrahedron Asymmetry, 1995,6,2123; Tetrahedron Lett.1995,35,7991].
2. the method that non-oxide coupling is synthetic
The coupling reaction of metal catalytic also can be used for the pure binaphthol derivative of synthesizing optical, Tamio Hayashi is with Ni catalyst coupling RMgBr and the synthetic binaphthol derivative [J.Am.Chem.Soc.1988 of bromobenzene reaction, 110,8153], its optical purity reaches as high as 95%.But the part that should react used is relatively more expensive, and its coupled product scope is subjected to certain restriction.Tomioka had also synthesized similar compound [J.Am.Chem.Soc.1992,114,8732] with nucleophilic substitution in 1992.Other also can be used for synthesizing the binaphthol derivative with chiral axis, [Chem.Commun, 2000,1723 with Suzuki reaction, Heck reaction; J.Am.Chem.Soc.2000,122,12051].The reaction of this class has a common feature, and the product scope is very restricted, and used part is difficult for synthetic, costs an arm and a leg and is difficult to a large amount of preparations, is difficult to guarantee optical purity when catalytic reaction is amplified.
3. oxidative coupling reaction
Oxidative coupling reaction is under the chiral catalyst catalysis with catalytic amount, with oxygen is oxidant, with the naphthols direct oxidation coupling of non-optical property for having optically active binaphthol and derivative thereof, because this type of reaction only needs the catalyst of catalytic amount, other oxidant and substrate more easily obtain, synthetic product scope mainly is optically pure binaphthol and the derivative thereof with extremely important function, therefore has been subjected to paying attention to widely.But the design of part and synthetic be difficult point always, the work of doing comparatively successfully at present that mainly contains following aspect: chirality Ru (the II)-imines class complex catalysis oxidative coupling naphthol derivative with photoactivation has obtained the binaphthol derivative [Synlett of 33～71% optical purities, 2000,14,333], the optical purity of this method is lower, is difficult to direct use; This class of the vanudium complex catalysis of chiral schiff base is reacted, and beta naphthal is also had only the highest 62% optical purity [Chem.Commun.2001,3,869; Org.Lett.2001,66,481].
The object of the present invention is to provide a kind of chiral catalyst that is used for oxidative coupling naphthol, can obtain the binaphthol and the derivative thereof of high-optical-purity.
The objective of the invention is to realize by following technical proposals:
The chiral catalyst that is used for oxidative coupling naphthol is characterized in that this chiral catalyst is schiff bases and the vanadium metal that chiral amino acid and chirality formoxyl binaphthol or derivatives thereof form
Complex compound, its structural formula is as follows: wherein R is benzyl, phenyl, isopropyl, isobutyl group and the tert-butyl group; The configuration of formoxyl binaphthol is R or S, and amino acid whose configuration is R or S; The kind of alcohol with whether have a catalytic performance that does not influence this catalyst.
In the such scheme; the preparation technology who is used for the chiral catalyst of oxidative coupling naphthol is: chiral amino acid and NaAc are dissolved in the water; stirred 5～15 minutes down at 40～80 ℃; again with 3; 3 '-diformyl binaphthol is dissolved in ethanol and the oxolane mixed solvent (ratio is 1: 1) and joins in the reactant mixture; be heated to 70～90 ℃ and allow it naturally cool to room temperature, adding concentration is 25% VOSO
4The aqueous solution reacts the chiral catalyst that i.e. generation in 1～5 hour is used for oxidative coupling naphthol; Wherein, chiral amino acid: NaAc: water: 3,3 '-diformyl binaphthol: VOSO
4Be 1: 2: 100～150: 0.5: 1 (ratio of amount of substance), mixed solvent: 3,3 '-diformyl binaphthol was 20～25: 1 (in mass).
In the such scheme, with the naphthols or derivatives thereof is raw material, is oxidant with oxygen, is used for the chiral catalyst of oxidative coupling naphthol in ratio (in the raw material) adding of 1～20mol%, carry out oxidative coupling reaction, promptly generate the binaphthol and the derivative thereof of high-optical-purity.
The present invention has changed the enantioselectivity of the single chiral centre control reaction of simple usefulness, the chirality of amino acid whose chirality and binaphthol combined allow the two common influence reaction, thereby the optical purity of product is brought up to 83～98%, and this is the best result that can reach so far.
The preparation route of the chiral catalyst that is used for oxidative coupling naphthol of the present invention is as follows:
This catalyst oxidative coupling naphthol has obtained the coupled product of high-optical-purity, and the preparation route is as follows:
Wherein, raw material has four kinds of 2a, 2b, 2c, 2d, 2a:R
1=R
2=R
3=H, 2b:R
1=H, R
2=H, R
3=OM, 2c:R
1=Br, R
2=H, R
3=H, 2d:R
1=H, R
2=OM, R
3=H; Corresponding product also has four kinds of 3a, 3b, 3c, 3d, 3a:R
1=R
2=R
3=H, 3b:R
1=H, R
2=H, R
3=OM (M represent methylidene), 3c:R
1=Br, R
2=H, R
3=H, 3d:R
1=H, R
2=OM, R
3=H; Catalyst also has four kinds of 1a, 1b, 1c, 1d, wherein, and 1a:R=Bn, 1b:R=
iPr, 1c:R=
iBu, 1d:R=
tBu, used 3,3 '-diformyl binaphthol is the R configuration, and used amino acid is the S configuration.
Be reflected under 0 ℃ and carry out, optical purity is measured by chirality Kromasil CHI-TBB HPLC.
Reaction result is as shown in the table:
Numbering product catalyst reaction time productive rate % E.e%
(my god)
1 3a 1b 8 86 81
2 3a 1c 6 95 83
3 3b 1b 5 85 97
4 3b 1c 5 88 98
5 3c 1b 5 98 87
6 3c 1c 5 99 88
7 3d 1b 7 - -
8 3d 1c 7 - -
Be embodiments of the invention below.
Embodiment one
2,2 '-dimethoxy-methyl-1, the preparation of 1-binaphthol
4.53g NaH (90mmole) is dissolved among 120mL THF and the 60mL DMF, ice bath is cooled to below 0 ℃, is added dropwise to the solution that 9.0g (31.5mmol) binaphthol is dissolved in 36mL THF, continue to stir 1 hour, be added dropwise to 8.7mL MOMCl (94.2mmol), remove ice bath, stirring is spent the night.Add 100mL water, revolve most of THF, with ethyl acetate extraction three times (100mL * 3), extract is with saturated common salt washing twice, through anhydrous Na
2SO
4Drying, filtration is spin-dried for, and gets the 11.5g product with the 150mL recrystallizing methanol again, yield: 97.3%.The physical constant of this compound is identical with document.
Embodiment two
2,2 '-dimethoxy-methyl-3,3 '-diformyl-1, the preparation of 1 '-binaphthol
In the 500mL round-bottomed flask, add 3.74g (10mmol) 2,2 '-dimethoxy-methyl-1, the 1-binaphthol is bled with Ar ventilation three times, adds ether dissolution.The BuLi solution that at room temperature adds 20mL1.6M stirred 3 hours, added the solution that 8.0mL DMF is dissolved in 8.0mL THF under the ice bath cooling.Stir and add saturated NH after 5 hours
4The Cl aqueous solution.Revolve most of organic solvent, to use ethyl acetate extraction three times (100mL * 3), extract is with saturated common salt washing twice, through anhydrous Na
2SO
4Drying, filtration is spin-dried for, and uses benzinum: ethyl acetate (3V: 1V) launch the 3.55g product, yield: 83%.
1HNMR(ppm)：2.88，s，6H；4.74，tr，4H；7.25，q，2H；7.44-7.50，4H；8.10，2H；8.63，2H；10.56，s，2H。The physical constant of this compound is identical with document.
Embodiment three
The preparation of chiral catalyst
The phenylalanine of 1mmol (S) configuration; 2mmol NaAc mixes; add 2mL water, substitute gas three times, 60 ℃ add (R)-2 behind the stirring 10min down; 2 '-dimethoxy-methyl-3; 3 '-diformyl-1,1 '-binaphthol (0.5mmol) is dissolved in the solution of 5mL ethanol and 5mLTHF, is heated to 80 ℃ and stirs 20min; slowly be cooled to 25 ℃ and stirred 2 hours, add 1mmol VOSO
4The aqueous solution continues to stir 2 hours, is spin-dried for organic solvent, and centrifugation obtains solid, with obtaining required chiral catalyst behind the organic solvent washing.1a:400mg, mass spectral analysis 1a:858 (M
+, 20), 813 (M-C
2H
5OH+H
+, 100), infrared analysis (cm
-1): ν
C=N(1673), ν
C=O(1614), ν
V=O(987).
Embodiment four
The preparation of chiral catalyst
The valine of 1mmol (S) configuration; 2mmol NaAc mixes; add 2mL water, substitute gas three times, 70 ℃ add (R)-2 behind the stirring 10min down; 2 '-dimethoxy-methyl-3; 3 '-diformyl-1,1 '-binaphthol (0.5mmol) is dissolved in the solution of 5mL ethanol and 5mL THF, is heated to 80 ℃ and stirs 20min; slowly be cooled to 25 ℃ and stirred 2 hours, add 1mmol VOSO
4The aqueous solution continues to stir 2 hours, is spin-dried for organic solvent, and centrifugation obtains solid, with obtaining required chiral catalyst behind the organic solvent washing.1b:320mg, mass spectral analysis: 762 (M
-, 20), 717 (M-C
2H
5OH+H
+, 100), infrared analysis: ν
C=N(1675), ν
C=O(1611), ν
V=O(988).
Embodiment five
The preparation of chiral catalyst
The isoleucine of 1mmol (S) configuration; 2mmol NaAc mixes, and adds 2mL water, substitutes gas three times; 60 ℃ add (R)-2 behind the stirring 10min down; 2 ,-dimethoxy-methyl-3,3 '-diformyl-1; 1 '-binaphthol (0.5mmol) is dissolved in the solution of 5mL ethanol and 5mLTHF; be heated to 80 ℃ and stir 20min, slowly be cooled to 25 ℃ and stirred 2 hours, add 1mmol VOSO
4The aqueous solution continues to stir 2 hours, is spin-dried for organic solvent, and centrifugation obtains solid, with obtaining required chiral catalyst behind the organic solvent washing.1c, 369mg, mass spectral analysis: 783 (M-C
2H
5OH+K
+, 100), 737 (M-
2C
2H
5OH+K
+, 38), infrared analysis: ν
C=N(1685), ν
C=O(1613), ν
V=O(982).
Embodiment six
The preparation of chiral catalyst
The new leucine of 1mmol (S) configuration; 2mmol NaAc mixes; add 2mL water, substitute gas three times, 60 ℃ add (R)-2 behind the stirring 10min down; 2 '-dimethoxy-methyl-3; 3 '-diformyl-1,1 '-binaphthol (0.5mmol) is dissolved in the solution of 5mL ethanol and 5mLTHF, is heated to 90 ℃ and stirs 20min; slowly be cooled to 25 ℃ and stirred 3 hours, add 1mmol VOSO
4The aqueous solution continues to stir 2 hours, is spin-dried for organic solvent, and centrifugation obtains solid, with obtaining required chiral catalyst behind the organic solvent washing.1d, 359mg, mass spectral analysis: 783 (M-C
2H
5OH+K
+, 100), 737 (M-
2C
2H
5OH+K
+, 38), infrared analysis: ν
C=N(1657), ν
C=O(1610), ν
V=O(985).
Embodiment seven
The reaction of chiral catalyst catalytically oxidative coupling naphthols and derivative thereof
In one or two neck flask, add chiral catalyst 1b 16mg (0.02mmol) and be dissolved in the dry CCl of 1mL
4Solution, in oxygen, stir 10min, add 28.8mg (0.2mol) naphthols, stirred 8 days at 0 ℃, after having reacted, the pressure reducing and steaming solvent, with using benzinum: ethyl acetate (3V: 1V) launch product 25mg.Nmr analysis: (300MHz, CDCl
3) δ (ppm) 7.98 (d, J=9.0Hz, 2H), 7.90 (d, J=7.8Hz, 2H), 7.38 (d, J=9.0Hz, 2H), 7.41-7.27 (m, 4H), 7.16 (d, J=8.4Hz, 2H), 5.09 (s, 2H). optical purity 81% (Kromasil CHI-TBB column, Hexane/propan-2-o1=4: 1; Flow rate 1mL/min; S-isomer, t
R5.81min and R-isomer, t
R6.44min)
Embodiment eight
The reaction of chiral catalyst catalytically oxidative coupling naphthols and derivative thereof
In one or two neck flask, add chiral catalyst 1c 16mg (0.02mmol) and be dissolved in the dry CCl of 1mL
4Solution, in oxygen, stir 10min, add 28.8mg (0.2mol) naphthols, stirred 6 days at 0 ℃, after having reacted, the pressure reducing and steaming solvent, with using benzinum: ethyl acetate (3V: 1V) launch product 27mg, optical purity: 83%.Analyze the same.
Embodiment nine
The reaction of chiral catalyst catalytically oxidative coupling naphthols and derivative thereof
In one or two neck flask, add chiral catalyst 1b 16mg (0.02mmol) and be dissolved in the dry CCl of 1mL
4Solution, in oxygen, stir 10min, add 35mg (0.2mol) 7-methoxyl group-beta naphthal, stirred 5 days at 0 ℃, after having reacted, the pressure reducing and steaming solvent, with using benzinum: ethyl acetate (3V: 1V) launch product 29mg, productive rate: 85%.Nmr analysis (300MHz, CDCl
3) δ (ppm) 7.88 (d, J=9.0Hz, 2H), 7.79 (d, J=9.0Hz, 2H), 7.22 (d, J=8.7Hz, 2H), 7.03 (dd, J=9.0Hz, 2.4Hz, 2H), 6.49 (d, J=2.4Hz, 2H), 5.08 (s, 2H), 3.59 (s, 6H).Optical purity: 97% (HPLC KromasilCHI-TBB column, Hexane/propan-2-ol=4: 1; Flow rate 1mL/min; S-isomer, t
R5.88min and R-isomer, t
R6.38min).
Embodiment ten
The reaction of chiral catalyst catalytically oxidative coupling naphthols and derivative thereof
In one or two neck flask, add chiral catalyst 1c 16mg (0.02mmol) and be dissolved in the dry CCl of 1mL
4Solution, in oxygen, stir 10min, add 35mg (0.2mol) 7-methoxyl group-beta naphthal, stirred 5 days at 0 ℃, after having reacted, the pressure reducing and steaming solvent, with using benzinum: ethyl acetate (3V: 1V) launch product 30mg, productive rate: 88%.Optical purity: 98%, analyze with 3).
Embodiment 11
The reaction of chiral catalyst catalytically oxidative coupling naphthols and derivative thereof
In one or two neck flask, add chiral catalyst 1b 16mg (0.02mmol) and be dissolved in the dry CCl of 1mL
4Solution, in oxygen, stir 10min, add 44mg (0.2mol) 6-bromo-beta naphthal, stirred 5 days at 0 ℃, after having reacted, the pressure reducing and steaming solvent, with using benzinum: ethyl acetate (3V: 1V) launch product 43mg, productive rate: 98%.Nmr analysis (300MHz, CDCl
3) δ (ppm) 8.06 (d, J=1.8Hz, 2H), 7.89 (d, J=9.0Hz, 2H), 7.37 (d, J=6.9Hz, 2H), 7.36 (dd, J=9.0Hz, 1.8Hz, 2H), 6.96 (d, J=9.0Hz, 2H), 5.08 (s, 2H).Optical purity: 88% (R) (HPLC Kromasil CHI-TBB column, Hexane/propan-2-ol=4: 1; Flow rate 1mL/min; S-isomer, t
R7.72minand R-isomer, t
R8.76min).
Embodiment 12
The reaction of chiral catalyst catalytically oxidative coupling naphthols and derivative thereof
In one or two neck flask, add chiral catalyst 1b 16mg (0.02mmol) and be dissolved in the dry CCl of 1mL
4Solution, in oxygen, stir 10min, add 47mg (0.2mol) 6-bromo-beta naphthal, stirred 5 days at 0 ℃, after having reacted, the pressure reducing and steaming solvent, with using benzinum: ethyl acetate (3V: 1V) launch product 46mg, productive rate: 99%.Optical purity: 88%.Analyze the same.
Embodiment 13
The reaction of chiral catalyst catalytically oxidative coupling naphthols and derivative thereof
In one or two neck flask, add chiral catalyst 1b 16mg (0.02mmol) and be dissolved in the dry CCl of 1mL
4Solution, in oxygen, stir 10min, add 40mg (0.2mol) 6-allyloxy-beta naphthal, stirred 6 days at 0 ℃, after having reacted, the pressure reducing and steaming solvent, with using benzinum: ethyl acetate (3V: 1V) launch product 32mg, productive rate: 80%.Nmr analysis (300MHz, CDCl
3) δ (ppm) 7.59 (d, J=9.0Hz, 2H, 2 * HC), 7.50 (d, J=9.0Hz, 2H, 2 * HC), 6.94 (d, J=9.0Hz, 2H, 2 * HC), 6.76 (dd, J=9.0Hz, 2.6Hz, 2H, 2 * HC), 6.19 (d, J=2.4Hz, 2H, 2 * HC), 5.56 (m, 2H), 4.81 (m, 2H), 4.85 (dd, J=12Hz, 1.5Hz), 4.00 (m, 4H).Optical purity: 79.6% (HPLCKromasil CHI-TBB column, Hexane/propan-2-ol=4: 1; Flow rate 1mL/min; The retention time of two isomers is respectively t
1=12.22 min, t
2=10.95min).
Claims (3)
1. the chiral catalyst that is used for oxidative coupling naphthol is characterized in that this chiral catalyst is chiral amino acid and the schiff bases of chirality formoxyl binaphthol or derivatives thereof formation and the complex compound of vanadium metal, and its structural formula is as follows:
Wherein R is benzyl, phenyl, isopropyl, isobutyl group and the tert-butyl group; The configuration of formoxyl binaphthol is R or S, and amino acid whose configuration is R or S; The kind of alcohol with whether have a catalytic performance that does not influence this catalyst.
2. the chiral catalyst that is used for oxidative coupling naphthol according to claim 1, the preparation technology who it is characterized in that being used for the chiral catalyst of oxidative coupling naphthol is: chiral amino acid and NaAc are dissolved in the water, stirred 5～15 minutes down at 40～80 ℃, again with 3,3 '-diformyl binaphthol is dissolved in ethanol and the oxolane mixed solvent (ratio is 1: 1) and joins in the reactant mixture, being heated to 70～90 ℃ allows it naturally cool to room temperature, adding concentration is 25% the VOSO4 aqueous solution, reacts promptly to generate the chiral catalyst that is used for oxidative coupling naphthol in 1～5 hour; Wherein, chiral amino acid: NaAc: water: 3,3 '-diformyl binaphthol: VOSO
4Be 1: 2: 100～150: 0.5: 1 (ratio of amount of substance), mixed solvent: 3,3 '-diformyl binaphthol was 20～25: 1 (in mass).
3. the chiral catalyst that is used for oxidative coupling naphthol according to claim 1 and 2, it is characterized in that with the naphthols or derivatives thereof be raw material, with oxygen is oxidant, ratio (in raw material) in 1～20mol% adds the chiral catalyst that is used for oxidative coupling naphthol, carry out oxidative coupling reaction, promptly generate the binaphthol and the derivative thereof of high-optical-purity.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102166530A (en) * | 2011-03-28 | 2011-08-31 | 上海大学 | Bi-chiral organic small molecular catalyst and preparation method thereof |
| CN103480418A (en) * | 2013-10-11 | 2014-01-01 | 苏州思睿屹新材料股份有限公司 | Chiral catalyst in binaphthol synthesis technology |
-
2002
- 2002-03-22 CN CNB021134898A patent/CN1176924C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102166530A (en) * | 2011-03-28 | 2011-08-31 | 上海大学 | Bi-chiral organic small molecular catalyst and preparation method thereof |
| CN102166530B (en) * | 2011-03-28 | 2013-03-06 | 上海大学 | Bi-chiral organic small molecular catalyst and preparation method thereof |
| CN103480418A (en) * | 2013-10-11 | 2014-01-01 | 苏州思睿屹新材料股份有限公司 | Chiral catalyst in binaphthol synthesis technology |
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