CN1887893A - New-type spiro phosphonite and its application in the asymmetrical catalytic hydrogenation of enamine - Google Patents
New-type spiro phosphonite and its application in the asymmetrical catalytic hydrogenation of enamine Download PDFInfo
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Abstract
The present invention relates to one new type of spiro phosphonite and its application in the asymmetrical catalytic hydrogenatin of enamine, and is especially the synthesis of one new type of chiral spiro phosphonite and its ionic rhodium complex and the application of the ionic rhodium complex in the asymmetrical catalytic hydrogenatin of non-functional enamine. The spiro phosphonite is prepared with spiro diphenol as material through one of tow processes. The spiro phosphonite has two optical isomers, dextral spiro phosphonite and levo spiro phosphonite, and the half and half mixture of the dextral spiro phosphonite and levo spiro phosphonite constitute racemic spiro phosphonite. The spiro phosphonite has wide application.
Description
Technical field
The present invention relates to the synthetic method of a kind of novel hand-type volution phosphinate and ionic rhodium complex thereof, and the application of complex compound in the asymmetric catalytic hydrogenation of non-functionalization enamine.Be exactly synthetic a kind of novel chiral volution monophosphorus ligand and corresponding chiral rhodium complex specifically, and this chiral rhodium complex is applied to the asymmetric catalytic hydrogenation reaction of prochiral non-functionalized enamine to prepare optically active tertiary amine with volution skeleton.When this invention provides a kind of method for preparing novel chiral volution monophosphorus ligand and corresponding rhodium complex, and the asymmetric catalytic hydrogenation reaction that is applied to non-functionalization enamine is with preparation optical activity tertiary amine.
Background technology
In organic synthesis and medicine were synthetic, optically pure amine was the very important chipal compounds of a class (Keay, J.D.in Comprehensive Organic Synthesis, Vol.8, Eds.:Trost, B.M.Fleming, I., Pergamon, Oxford, 1991. (b) Comprehensive NaturalProducts Chemistry, Vols.1-9, Eds.:Barton, D.H.R.Nakanishi, K.Meth-Cohn, O., Elsevier, Oxford, 1999).Therefore develop this optically pure aminated compounds method of asymmetric synthesis and caused the great interest of researcher, and developed and some synthetic method of Chiral Amine compounds (Tang, W.-J efficiently; Zhang, X.-M.Chem.Rev.2003,103,3029).In these synthetic methods, it is one of the highest synthetic method of Atom economy with fixed attention that the asymmetric catalytic hydrogenation of prochirality enamine compound does not have.Up to the present, the asymmetric catalytic hydrogenation of the prochirality enamine of most bibliographical informations mainly concentrates on the asymmetric catalytic hydrogenation of the enamides that contains coordinating group (as: ethanoyl etc.).And, have only this alkene acid amides that contains acyl group in hydrogenation, could obtain outstanding chiral induction.And for not containing acyl group, i.e. the asymmetric catalytic hydrogenation of non-functionalized enamine, successful example is fewer.1994, Buchwald was applied to 1 with the Chiral Titanium catalyzer, and the asymmetric hydrogenation of 1-two substituted enamine compounds has obtained being up to Chiral Amine compounds (Lee, the N.E. of 98%ee; Buchwald, S.L.J.Am.Chem.Soc.1994,116,5985).2000, people such as B rner use rhodium/diphosphine ligand complex as catalyzer to 1, the catalytic hydrogenation of 1-two substituted enamines is studied, and has obtained being up to chirality amine product (Tararov, the V.I. of 72%ee; Kadyrov, R.; Riermeier, T.H.; Holz, J.; B rner, A.Tetrahedron Lett.2000,41,2351).Therefore, synthetic novel chiral phosphine part and the catalyzer that is suitable for the non-functionalized enamine of asymmetric catalytic hydrogenation, directly obtains corresponding chirality tertiary amine of design has very high Research Significance and using value.
Summary of the invention
The objective of the invention is to disclose a kind of novel monophosphorous ligand---volution phosphinate and preparation method thereof with spiro indan skeleton;
Another object of the present invention also is rhodium complex that discloses a kind of preparation of being set out by above-mentioned volution phosphinate and preparation method thereof;
Purpose of the present invention also comprises and discloses a kind of synthetic by novel chiral volution phosphinate and rhodium complex thereof, for the asymmetric catalytic hydrogenation of the non-functionalized enamine of prochirality provides chiral ligand and catalyzer; For chirality tertiary amine synthetic provides more efficiently, synthetic method high enantioselectivity, more economical.
Have the novel volution phosphinate that general formula is I for realizing purpose of the present invention, at first having synthesized:
In the general formula I: n=0～3; R
1, R
2Be H, C
1～C
8Alkyl, C
1～C
8Alkoxyl group, two-(C
1～C
8Alkyl)-amino, or two adjacent (when n 〉=2) R
1, R
2For and alicyclic ring or aromatic ring; R
1And R
2Can be identical, also can be different.
R
3, R
4, R
5, R
6Be H, C
1～C
8Alkyl, C
1～C
8Alkoxyl group or aryl, or R
3～R
4, R
5～R
6For and alicyclic ring or aromatic ring; R
3, R
4, R
5, R
6Can be identical, also can be different.
R
7Be C
1～C
8Alkyl, C
1～C
8Cycloalkyl, aryl or substituted aryl.
Spiro indan structure in the described volution phosphinate of general formula I has axial chirality, so have two optically active isomers, one is a dextrorotation volution phosphinate, and it two is left-handed volution phosphinate, and the equal amount of mixture of these two optically active isomers then becomes racemize volution phosphinate.Therefore, in fact the said volution phosphinate of the present invention comprises racemic modification, dextrorotatory form and levo form.Racemic modification, dextrorotatory form and levo form have identical chemical structure of general formula, but have different three-dimensional arrangements and rotary light performance.
New-type spiro phosphinate described in the general formula I can be synthetic by following two kinds of methods.
First method:
With volution diphenol (SPINOL) under the effect of alkali and the alkyl phosphorus dichloride be 1: 1～4 with mol ratio, toluene is solvent, reacts under the room temperature to generate the volution phosphinate in 12～24 hours.
Second method:
Is 1: 1～4 with volution diphenol (SPINOL) and phosphorus trichloride with mol ratio, and temperature-20～80 a ℃ following reaction generated the intermediate phosphoryl chloride in 1～24 hour, and temperature generated the volution phosphinate in 1～24 hour at-78～-20 ℃ of following Yu Geshi reagent reacts then.
Institute of the present invention synthetic chiral rhodium complex is to have the rhodium complex that general formula is the chiral spiro phosphinate of II:
Among the general formula I I: n=0～3; R
1, R
2Be H, C
1～C
8Alkyl, C
1～C
8Alkoxyl group, two-(C
1～C
8Alkyl)-amino, or two adjacent (when n 〉=2) R
1, R
2For and alicyclic ring or aromatic ring; R
1And R
2Can be identical, also can be different.
R
3, R
4, R
5, R
6Be H, C
1～C
8Alkyl, C
1～C
8Alkoxyl group or aryl, or R
3～R
4, R
5～R
6For and alicyclic ring or aromatic ring; R
3, R
4, R
5, R
6Can be identical, also can be different.
R
7Be C
1～C
8Alkyl, C
1～C
8Cycloalkyl, aryl or substituted aryl.
X is Cl, Br, I, BF
4, PF
6, SbF
6
The preparation method of the rhodium complex of chiral spiro phosphinate described in the general formula I I is characterized in that it is by following method preparation: under nitrogen or argon shield, and under the room temperature condition, 1 normal rhodium metal precursor (as: [Rh (COD) Cl]
2, Rh (COD)
2BF
4, Rh (acac) (CH
2CH
2)
2, Rh (COD)
2PF
6, Rh (COD)
2SbF
6, Rh (COD)
2OTf, [Rh (COD) (CH
3CN)] BF
4, Rh (acac) (CO)
2, [RhCl (CH
2CH
2)]
2) made in 0.5～3 hour with the complex reaction in the THF solvent of 2～3 normal chiral monophosphorous ligands.The not purified asymmetric hydrogenation that is directly used in of prepared catalyzer.
Of the present invention have a rhodium complex that general formula is II, and the asymmetric catalytic hydrogenation that is applied to the prochirality enamine reacts and obtains optically pure tertiary amine.This method has efficient, economic advantage at the chirality tertiary amine that obtains high enantioselectivity simultaneously.
Wherein:
R
8, R
9, R
10Be C
1～C
8Alkyl, cycloalkyl, aryl.
Term " C
1～C
8Alkyl " the expression straight or branched contain the alkyl of 8 carbon atoms at the most, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, neo-pentyl, hexyl, uncle's hexyl, heptyl, different heptyl, octyl group and iso-octyl.Similarly, " C
1～C
8Alkoxyl group " represent alkyl as hereinbefore defined by the Sauerstoffatom connection, as methoxyl group, oxyethyl group, propoxy-, butoxy etc.The substituting group that " aryl " expression has aromatic ring structure character, as phenyl, furyl, thienyl, pyridyl, quinolyl, indyl, and the aryl that has different substituents on the aromatic ring, as: p-methylphenyl, p-methoxyphenyl, rubigan etc.
Preparation chirality tertiary amine of the present invention specify as follows:
Under nitrogen or argon shield; in appropriate solvent (as methylene dichloride, tetrahydrofuran (THF), toluene, ethyl acetate, normal hexane, methyl alcohol, ethanol, DMF, DMSO); adopt on-the-spot 0.001～0.05 normal chiral catalyst II that generates, and add 0.01～0.1 normal I
2With 0.05～1.0 normal AcOH, the reaction room temperature is under 0～60 ℃ the reaction conditions, and the non-functionalized enamine of prochirality is in being filled with the hydrogenation still of 1～100atm hydrogen, and stirring reaction 12～48 hours is to obtain chirality tertiary amine with certain optical purity.
The present invention has synthesized the asymmetric catalytic hydrogenation reaction that the chirality phosphorous acid ester with volution skeleton also is used for the rhodium complex of this compound non-functionalized enamine compound, has developed a kind of economy of chirality tertiary amine, suitable method of preparing efficiently.Spiro indan structure in this volution phosphinate has axial chirality, therefore this compounds has two optically active isomers: dextrorotation volution phosphinate and left-handed volution phosphinate, the equal amount of mixture of these two optically active isomers then becomes racemize volution phosphinate.Volution phosphinate of the present invention is a kind of purposes compound very widely, as can be used as chiral ligand, and the asymmetric catalytic hydrogenation that its corresponding chiral rhodium complex is used for the prochirality enamine prepares the chirality tertiary amine (the e.e. value is up to 99.9%) of high-optical-purity.
Embodiment
The present invention further illustrates by following embodiment, but following embodiment only helps further to understand the present invention, does not limit content of the present invention.Preparation method of the present invention can be further as follows with the preparation process embodiment of representation compound:
Embodiment 1
(S)-and O, the preparation of O '-[7,7 '-(1,1 '-spiro indan)]-tertiary butyl phosphorous acid ester (Ia)
Under nitrogen atmosphere, in the 10mL degassed toluene solution of the tertiary butyl dichloride phosphine that 169mg (1.1mmol) is housed, slowly drip the 10mL toluene of 252mg (1.0mmol) and the solution of 2mL ethamine under the room temperature, stirring at room 12 hours, the anhydrous and oxygen-free diatomite filtration, the decompressing and extracting solvent gets product 254mg, yield 75%.[α]
20 D-456.7(c1.2，CH
2Cl
2).
1H NMR(CDCl
3，400MHz)：δ0.936(d，J＝13.2Hz，9H，CH
3)，1.91-2.06(m，2H，CH
2)，2.12-2.25(m，2H，CH
2)，2.80-2.85(m，2H，CH
2)，3.01-3.16(m，2H，CH
2)，6.85-7.23(m，6H，Ar-H)，
31P NMR(CDCl
3，161MHz)：δ179.04.
13C NMR(CDCl
3，100MHz)：δ150.9，147.6，147.5，145.6，145.5，141.4，140.2，129.1，127.9，121.8，121.4，121.1，120.7，59.6，38.6，38.3，36.3，35.9，31.0，30.6，24.2，24.1.HRMS(EI)Calcd for C
21H
23O
2P：338.1436.Found：338.1438.
Embodiment 2
(S)-and O, the preparation of O '-[7,7 '-(1,1 '-spiro indan)]-sec.-propyl phosphorous acid ester (Ib)
Under nitrogen atmosphere, in the 10mL degassed toluene solution of the sec.-propyl dichloride phosphine that 159mg (1.1mmol) is housed, slowly drip the 10mL toluene of 252mg (1.0mmol) and the solution of 2mL ethamine under the room temperature, stirring at room 12 hours, the anhydrous and oxygen-free diatomite filtration, the decompressing and extracting solvent gets product 195mg, yield 60%.[α]
20 D-562.0(c1.0，CH
2Cl
2).
1H NMR(CDCl
3，400MHz)：δ1.048(dd，3H，J＝13.2，7.2Hz，CH
3)，1.223(dd，3H，J＝17.6，7.2Hz，CH
3)，1.65-1.62(m，1H，CH)，2.03-2.00(m，2H，CH
2)，2.27-2.20(m，2H，CH
2)，2.92-2.84(m，2H，CH
2)，3.11-3.07(m，2H，CH
2)，6.84(d，1H，J＝8.0Hz，Ar-H)，6.94(d，1H，J＝8.0Hz，Ar-H)，7.09-7.06(m，2H，Ar-H)，7.27-7.16(m，2H，Ar-H).
31P NMR(CDCl
3，161MHz)：δ184.70.
13C NMR(CDCl
3，100MHz)：δ150.6，146.3，146.2，146.0，145.4，142.2，140.8，129.1，127.9，121.5，121.2，120.8，59.4，38.7，38.2，31.1，30.8，28.2，27.9，16.3，16.0，15.9，15.7.HRMS(EI)Calcd for C
20H
21O
2P：324.1282.Found：324.1279.
Embodiment 3
(R)-and O, the preparation of O '-[7,7 '-(1,1 '-spiro indan)]-methyl phosphorous acid ester (Ic)
Under nitrogen atmosphere, to be equipped with 308mg (1.2mmol) (R)-add 263mg (2.6mmol) triethylamine in the volution diphenol, 15mL reaction of toluene bottle, stir down and in reaction flask, drip phosphorus trichloride 178mg (1.3mmol) in 0 ℃, again room temperature reaction 20 hours, through diatomite filtration, drain solvent after, squeeze into 20mL degassed toluene dissolving, temperature control slowly drips the CH of 3.16M at-78 ℃
3MgBr diethyl ether solution 0.36mL, low-temp reaction 6 hours rises to room temperature, reacted 2 hours, the anhydrous and oxygen-free diatomite filtration, the decompressing and extracting solvent gets product 134mg, yield 45%.[α]
20 D-664.1(c 1.0，CH
2Cl
2).
1H NMR(CDCl
3，400MHz)：δ1.18(d，3H，J＝11.2Hz，CH
3)，2.01-1.99(m，2H，CH
2)，2.24-2.21(m，2H，CH
2)，2.88-2.82(m，2H，CH
2)，3.08-3.04(m，2H，CH
2)，6.69(d，1H，J＝8.0Hz，Ar-H)，6.93(d，1H，J＝8.0Hz，Ar-H)，7.09-7.06(m，2H，Ar-H)，7.25-7.14(m，2H，Ar-H).
31P NMR(CDCl
3，161MHz)：δ180.30.
13C NMR(CDCl
3，100MHz)：δ150.3，145.9，145.5，142.3，141.0，130.1，129.1，127.6，122.2，121.6，121.3，120.8，59.4，38.6，38.3，31.1，30.8，19.8，19.5.HRMS(EI)Calcd for C
18H
17O
2P：296.0968.Found：296.0966.
Embodiment 4
The asymmetric catalytic hydrogenation synthesis of chiral tertiary amine of enamine
In the hydrogenation still, add 0.005mmol Rh (COD)
2BF
40.011mmol part (S)-Ia, add the 3.4mL tetrahydrofuran (THF) with syringe, room temperature complexing 20 minutes, add the THF solution (6.7mg/mL) of 0.4mL iodine and the THF solution (31mg/mL) of 0.2mL acetic acid successively, the enamine IV that adds 0.5mol at last, under the 10atm hydrogen-pressure, stirring at room hydrogenation 12 hours.Decompression removes solvent, separates obtaining target product through silica gel column chromatography.The transformation efficiency of GC assay determination reaction is 100%.The optical purity of HPLC assay products the results are shown in Table 1.
Table 1
| Sequence number | Enamine | Ee.(％) c | ||
| R 8 | R 9 | R 10 | ||
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 | C 6H 5 4-MeC 6H 4 3-MeC 6H 4 2-MeC 6H 4 4-MeOC 6H 4 3，4-(MeO) 2C 6H 3 C 6H 5 C 6H 5 C 6H 5 C 6H 5 C 6H 5 C 6H 5 C 6H 5 3-MeC 6H 4 4-MeOC 6H 4 4-MeOC 6H 4 | C 6H 5 C 6H 5 C 6H 5 C 6H 5 C 6H 5 C 6H 5 2-MeC 6H 4 2-ClC 6H 4 3-ClC 6H 4 4-ClC 6H 4 4-BrC 6H 4 4-FC 6H 4 2-FC 6H 4 4-FC 6H 4 4-FC 6H 4 4-ClC 6H 4 | -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- -(CH 2) 4- | 87 91 90 90 95 99 94 93 90 96 97 ＞99.9 85 90 95 93 |
Claims (10)
1. novel volution phosphinate is characterized in that having the compound of following structural formula:
In general formula I: n=0～3; R
1, R
2Be H, C
1～C
8Alkyl, C
1～C
8Alkoxyl group, two-(C
1～C
8Alkyl)-amino, or two adjacent (when n 〉=2) R
1, R
2Can be by being and alicyclic ring or aromatic ring; R
1And R
2Can be identical, also can be different;
R
3, R
4, R
5, R
6Be H, C
1～C
8Alkyl, C
1～C
8Alkoxyl group or aryl, or R
3～R
4, R
5～R
6For and alicyclic ring or aromatic ring; R
3, R
4, R
5, R
6Can be identical, also can be different;
R
7Be C
1～C
8Alkyl, C
1～C
8Cycloalkyl, aryl or substituted aryl.
2. the preparation method of the described New-type spiro phosphinate of claim 1 is characterized in that it is is starting raw material with the volution diphenol, makes by following method, and its reaction expression is as follows:
3. according to the preparation method of the described New-type spiro phosphinate of claim 2, it is characterized in that with the volution diphenol under the effect of alkali and alkyl dichloride phosphine be 1: 1～4 with mol ratio, react under the room temperature and generated the volution phosphinate in 12～24 hours.
4. the preparation method of the described New-type spiro phosphinate of claim 1 is characterized in that it is is starting raw material with the volution diphenol, makes by following method, and its reaction expression is as follows:
5. according to the preparation method of the described New-type spiro phosphinate of claim 4, it is characterized in that be 1: 1～4 with volution diphenol and phosphorus trichloride with mol ratio, temperature-20～80 a ℃ following reaction generated the intermediate phosphoryl chloride in 1～24 hour, and temperature generated the volution phosphinate in 1～24 hour at-78～-20 ℃ of following Yu Geshi reagent reacts then.
6. by the set out a kind of rhodium complex of novel chiral volution phosphinate of preparation of novel according to claim 1 volution phosphinate, it is characterized in that it being compound with following structural formula:
In general formula I I: n=0～3; R
1, R
2Be H, C
1～C
8Alkyl, C
1～C
8Alkoxyl group, two-(C
1～C
8Alkyl)-amino, or two adjacent (when n 〉=2) R
1, R
2For and alicyclic ring or aromatic ring; R
1And R
2Can be identical, also can be different;
R
3, R
4, R
5, R
6Be H, C
1～C
8Alkyl, C
1～C
8Alkoxyl group or aryl, or R
3～R
4, R
5～R
6For and alicyclic ring or aromatic ring; R
3, R
4, R
5, R
6Can be identical, also can be different;
R
7Be C
1～C
8Alkyl, C
1～C
8Cycloalkyl, aryl;
X is Cl, Br, I, BF
4, PF
6, SbF
6
7. the preparation method of the rhodium complex of the described novel chiral volution of claim 6 phosphinate is characterized in that it is by following method preparation: under nitrogen or argon shield, under the room temperature condition, 1 normal rhodium metal precursor is as [Rh (COD) Cl]
2, Rh (COD)
2BF
4, Rh (acac) (CH
2CH
2)
2, Rh (COD)
2PF
6, Rh (COD)
2SbF
6, Rh (COD)
2OTf, [Rh (COD) (CH
3CN)] BF
4, Rh (acac) (CO)
2Or [RhCl (CH
2CH
2)]
2With 2～3 normal chiral monophosphorous ligands in solvent, complex reaction 0.5～3 hour and making.
8. according to the preparation method of the rhodium complex of the said novel chiral volution of claim 7 phosphinate, it is characterized in that described solvent is: a kind of or mixed solvent in methylene dichloride, tetrahydrofuran (THF), toluene, ethyl acetate, normal hexane, methyl alcohol, ethanol, DMF, the DMSO solvent.
9. the application of the rhodium complex of the described novel chiral volution of claim 6 phosphinate is characterized in that described ionic rhodium complex is used for the catalytic hydrogenation of prochirality olefinic amine compound as catalyzer in solvent; Catalyst levels is 1%～0.01%, and hydrogen pressure is in the hydrogenation still of 1～100atm, and temperature of reaction is 0～60 ℃, and the reaction times is 6 hours～48 hours;
Wherein:
10. according to the application of the rhodium complex of the said novel chiral volution of claim 9 phosphinate, it is characterized in that described solvent is: a kind of or mixed solvent in methylene dichloride, tetrahydrofuran (THF), toluene, ethyl acetate, normal hexane, methyl alcohol, ethanol, DMF, the DMSO solvent.
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| US10565015B2 (en) | 2017-09-18 | 2020-02-18 | The Regents Of The University Of Michigan | Spiroketal-based C2-symmetric scaffold for asymmetric catalysis |
| CN108659046B (en) * | 2018-05-11 | 2020-04-10 | 浙江大学 | Monophosphine ligand based on tetramethyl spiroindane skeleton, intermediate thereof, preparation method and application |
| WO2019213987A1 (en) * | 2018-05-11 | 2019-11-14 | 浙江大学 | Monophosphine ligand based on tetramethyl spirobiindane skeleton and intermediate thereof, and preparation method therefor and use thereof |
| CN108659046A (en) * | 2018-05-11 | 2018-10-16 | 浙江大学 | Monophosphorus ligand and its intermediate and preparation method based on tetramethyl spiro indan skeleton and purposes |
| US11377457B2 (en) * | 2018-05-11 | 2022-07-05 | Zhejiang University | 3,3,3',3'-tetramethyl-1,1'-spirobiindane-based monophosphine ligand, intermediates thereof, preparation method and use of the same |
| CN111620911A (en) * | 2020-06-05 | 2020-09-04 | 南开大学 | Chiral spiro-bis-rhodium phosphate complex and preparation method and application thereof |
| CN115246767A (en) * | 2021-04-26 | 2022-10-28 | 惠州凯特立斯科技有限公司 | Synthesis method of spiro diphenol with large steric hindrance and diphosphonite compound thereof |
| CN115246765A (en) * | 2021-04-26 | 2022-10-28 | 惠州凯特立斯科技有限公司 | Preparation method and application of spirocyclic diphenol and diphosphonite thereof |
| CN115246765B (en) * | 2021-04-26 | 2024-07-05 | 广东欧凯新材料有限公司 | Preparation method and application of spiro diphenol and biphosphinate thereof |
| CN113527066A (en) * | 2021-06-10 | 2021-10-22 | 香港科技大学深圳研究院 | Chiral spiro compound and preparation method and application thereof |
| CN113527066B (en) * | 2021-06-10 | 2024-02-20 | 香港科技大学深圳研究院 | Chiral spiro compound and preparation method and application thereof |
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