CN101168549A - 1,1'-biphenyls axial chirality diphosphinidene amide ligand connected at 5,5' position - Google Patents
1,1'-biphenyls axial chirality diphosphinidene amide ligand connected at 5,5' position Download PDFInfo
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- CN101168549A CN101168549A CNA2007101707749A CN200710170774A CN101168549A CN 101168549 A CN101168549 A CN 101168549A CN A2007101707749 A CNA2007101707749 A CN A2007101707749A CN 200710170774 A CN200710170774 A CN 200710170774A CN 101168549 A CN101168549 A CN 101168549A
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Abstract
The invention relates to 1, 1(1)-diphenyl axial chiral bis di-phosphinous amide ligand connected at 5,5(1) position in the chemical technical field. The structural formula of the invention is shown as follows: in the formula, n is equal to 5, 6, 7, 8, 9, 10, 11, or 12; R1 is equal to hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkyl of 1-8 carbon, or the alkoxyl of the 1-8 carbon; R2 is equal to the hydrogen, the fluorine, the chlorine, the bromine, the iodine, the trifluoromethyl, the alkyl of the 1-8 carbon, or the alkoxyl of the 1-8 carbon; R3 is equal to the hydrogen, the fluorine, the chlorine, the bromine, the iodine, the trifluoromethyl, the alkyl of the 1-8 carbon, or the alkoxyl of the 1-8 carbon; R4 is equal to the hydrogen, the fluorine, the chlorine, the bromine, the iodine, the trifluoromethyl, the alkyl of the 1-8 carbon, or the alkoxyl of the 1-8 carbon; R5 is equal to the hydrogen, the fluorine, the chlorine, the bromine, the iodine, the trifluoromethyl, the alkyl of the 1-8 carbon, or the alkoxyl of the 1-8 carbon; the ligand can be appliable to various unsymmetrical reactions catalyzed by metal, and have very high reaction activity and stereoselectivity.
Description
Technical field
The present invention relates to a kind of compound of chemical technology field, specifically, relate to 1 of a kind of 5,5 ' connection, 1 '-diphenyl axially chiral bi-phosphoramide part.
Background technology
Asymmetry catalysis synthetic key is how to design and the chiral catalyst of synthetic highly selective and catalytic activity, and wherein chiral ligand is the source that catalyzer produces asymmetric induction and control.C
2The type chiral diphosphine ligand is because the singularity of its structure is widely used in the asymmetric hydrogenation of metal catalytic, as the asymmetric catalytic hydrogenation reaction of alkene, allyl group alkylated reaction or the like.Through the development over 30 years, existing a large amount of biphosphine ligand emerges.The axial chirality diphosphine ligand BINAP that contains binaphthyl structure through years of researches accumulation successfully is applied to suitability for industrialized production to have on optically active compound.When BINAP occurred, scientists just was devoted to obtain to have good asymmetric reaction, selectivity, can come the synthetic part by easier method again.A class that wherein is subjected to studying energetically is exactly the phosphoramide part.1980, Hashimoto group has just found that the Space of binaphthyl structure has important effect in asymmetric induction, and in order to overcome the inconvenience of biphosphine ligand BINAP on synthesizing, this group proposes to utilize the dinaphthalene skeleton to obtain the biphosphine ligand of derivative type.Because the dinaphthalene diamines is easy to just can split, so just can be synthesized to dinaphthalene bi-phosphoramide part from the dinaphthalene diamines easily.Thereafter, they have also synthesized and have had substituent bi-phosphoramide part on the N atom, and study its asymmetric induction effect
Find through literature search prior art, Jean-Pierre Gen ê t is at " Eur.J.Org.Chem. " (European organic chemistry) 2003, the Synthesis and MolecularModeling Studies of SYNPHOS that delivers on the pp.1931-1941, a New, Efficient Diphosphane Ligand ForRuthenium-Catalyzed Asymmetric Hydrogenation " (a kind of in the ruthenium catalysis asymmetry hydrogenation reaction novel and effective biphosphine ligand SYNPHOS the research of synthetic and molecular model); the design concept of the axle chirality ligand that proposes in this article is to add two bigger groups at biaryl standard shaft ortho position; the steric hindrance by them obtains stable axle chirality; but limited the rotating angle of biphenyl equally, promptly limited the interfacial angle of biaryl standard shaft.And the size of interfacial angle has been proved catalytic activity and the selectivity that affects asymmetric catalysis in the document.Yet the research that contains the reactive behavior of the right title catalyzed reaction of interfacial angle size of bi-phosphoramide class part of a chirality and enantioselectivity is report not also.The axially chiral bi-phosphoramide class part of design and synthesizing new is studied an influence of the right title catalyzed reaction of interfacial angle and is had important science and realistic meaning for this reason.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of 5,1 of 5 ' connection, 1 '-diphenyl axially chiral bi-phosphoramide part, broken through the design concept of present axle chirality ligand, be applied to asymmetric catalysis and obtain high reactive behavior and stereoselectivity,, filter out axially chiral bi-phosphoramide part with better asymmetry catalysis effect by adjusting to interfacial angle.
The present invention is achieved by the following technical solutions, the invention provides 1 of a kind of 5,5 ' connection, 1 '-diphenyl axially chiral bi-phosphoramide ligand i, and the structural formula of this part is as follows:
In the formula: n=5,6,7,8,9,10,11 or 12;
R
1=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
2=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
3=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
4=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
5=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon.
Above-mentioned part can be that axle has (R) or (S) the enantiomer compound of configuration, and its structural formula is following II, III respectively:
N wherein, R
1, R
2, R
3, R
4, R
5As previously mentioned.
The present invention above-mentioned 5,1 of 5 ' connection, 1 '-diphenyl axially chiral bi-phosphoramide part, its synthetic method is: with 3-bromo-4-Nitroanisole is that raw material obtains compound V by Liv Ullmann linked reaction and recrystallization, and compound V demethylation obtains compound VI.Then compound VI by with alkylene dihalide (X (CH
2)
nX ') reaction obtains 5,5 ' (R) that the position links and (S) configuration blended compound VI I, and compound VI I is reduced into diamine compound VIII with Pd/C.Compound VIII is by obtaining (R) and (S) the bi-phosphoramide ligand i of configuration with the reaction of various aryl phosphines then.The bi-phosphoramide ligand i obtains (R) and (S) the optical purity target compound II and the III of two kinds of configurations through chiral separation.
Above-claimed cpd IV-VI of the present invention and axle have (R) and (S) structural formula of the compound VI I of configuration and VIII is as follows:
Axle has the compound VI I of (R) configuration and the structural formula of VIII is:
Axle has the compound VI I of (S) configuration and the structural formula of VIII is:
N as previously mentioned in the said structure.
The present invention contains the axle chirality of biphenyl class, has broken through the design concept of present axle chirality ligand, makes the variation range of its interfacial angle become and can regulate, thereby can filter out the axially chiral bi-phosphoramide part with better asymmetry catalysis effect.Such part can be applicable in the asymmetric reaction of various metal catalytics, as the reaction of the asymmetric catalytic hydrogenation of alkene, allyl group alkylated reaction or the like, has very high reactive behavior (can reach 100%) and stereoselectivity (can reach more than 90%).
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
(1) prepares compound V from 3-bromo-4-Nitroanisole
With compound VI (3.2g, 13.9mmol) and activated copper powder (3.6g 55.6mmol) is heated to 170 ℃ together, reacts four hours.Use the washing of benzene and ethyl acetate, boil off solvent, resistates acetonitrile recrystallization gets product V (1.7g, 80%).
1H?NMR(400MHz，CDCl
3)8.28(d，J＝8.8，2H)，7.00(dd，J＝9.2，2H)，6.70(d，J＝2，8，2H)，3.90(s，1H)
(2) prepare compound VI from compound V
(1.2g, 4.1mmol) (1.0g, 24.5mmol) at N, reflux is 12 hours in the dinethylformamide with Lithium chloride (anhydrous) for compound V.Add 10% sodium hydroxide solution, mixture washs with anhydrous diethyl ether, and water washs water with anhydrous diethyl ether again with 10% hydrochloric acid soln acidifying afterwards.Organic phase saturated common salt water washing, anhydrous sodium sulfate drying.Remove by filter siccative, boil off solvent and promptly get product VI (1.0g, 90%).
1H?NMR(400MHz，d-DMSO)11.14(s，2H)，8.16(d，J＝8.8，2H)，6.96(dd，J＝9.6，2H)，6.65(d，J＝2.4，2H)
(3) prepare compound VI I from compound VI
With compound VI (0.7g, 2.4mmol), (1.7 g, 12.5mmol) and 1, (98%, 0.5mL 2.5mmol) adds to 200mL N to the hot dibromo of 8-to Anhydrous potassium carbonate, in the dinethylformamide solution, at room temperature stirs 72h.With reacting liquid filtering, N is divided exactly in decompression, and dinethylformamide is crossed post with ethyl acetate and sherwood oil and obtained product VII (0.3g, 35%).
1H?NMR(400MHz，CDCl
3)8.23(d，J＝9.6，2H)，7.01(dd，J＝9.2，2H)，6.75(d，J＝2.8，2H)，4.39(m，2H)，4.20(m，2H)，1.95(m，2H)，1.64(m，2H)，1.34(m，8H)
(4) prepare compound VIII from compound VI I
With compound VI I (0.8g, 2.2mmol), palladium carbon (10%, 0.4g) be dissolved under the nitrogen atmosphere in the ethyl acetate (20mL), add the hydrogen reaction 12 hours of 5 air pressure.Remove by filter unnecessary palladium carbon, boil off solvent and promptly obtain product VII I (0.7g, 100%).
1H?NMR(400MHz，CDCl
3)6.82-6.75(m，6H)，4.20(m，2H)，4.00(m，2H)，1.89(m，2H)，1.62(m，3H)，1.42(m，8H).
(5) prepare Compound I (R1=R2=R3=R4=R5=H) from compound VIII
With compound VIII (0.3g, 0.9mmol), the purified triethylamine (1.1mL 7.4mmol) is dissolved in the purified dichloromethane solution, splash under the nitrogen atmosphere ice-water bath condition diphenyl phosphine chloride (0.4g, 2.0mmol), back flow reaction 12 hours.Reaction finishes back evaporate to dryness methylene dichloride, crosses post with ethyl acetate and sherwood oil and obtains product I (0.51g, 81%).
1H?NMR(400MHz，CDCl
3)7.27-7.12(m，22H)，6.83(dd，J＝8，J＝2.4，2H)，6.73(d，J＝2.4，2H)，4.52(d，J＝6，2H)，4.18(m，2H)，4.00(m，2H)，1.87(m，2H)，1.59(m，3H)，1.34(m，8H).
31P?NMR(CDCl
3，161MHz)34.24
5) prepare optical purity target compound II and III (R1=R2=R3=R4=R5=H) from Compound I
(0.51g 0.73mmol) splits and obtains (R) and (S) optical pure compound II of two kinds of configurations (0.22g, 86%) and III (0.21g, 82%) with Compound I to adopt chiral high performance liquid chromatography.
1H?NMR(400MHz，CDCl
3)7.27-7.12(m，22H)，6.83(dd，J＝8，J＝2.4，2H)，6.73(d，J＝2.4，2H)，4.52(d，J＝6，2H)，4.18(m，2H)，4.00(m，2H)，1.87(m，2H)，1.59(m，3H)，1.34(m，8H).
31P?NMR(CDCl
3，161MHz)34.24。
This embodiment synthetic method is simple, and total recovery can reach more than 20%.Prepared axle chirality ligand can with the asymmetric catalytic hydrogenation reaction of metallic ion coordination catalysis such as rhodium, ruthenium such as alkene, allyl group alkylated reaction or the like.
Claims (2)
1. one kind 5,1 of 5 ' connection, 1 '-diphenyl axially chiral bi-phosphoramide part is characterized in that, structural formula is as follows:
In the formula: n=5,6,7,8,9,10,11 or 12;
R
1=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
2=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
3=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
4=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
5=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon.
2. as claimed in claim 15,5 ' connect 1,1 '-diphenyl axially chiral bi-phosphoramide part is characterized in that, described bi-phosphoramide part is that axle has (R) and (S) diastereomeric compound of configuration, its structural formula is as follows:
In the formula: n=5,6,7,8,9,10,11 or 12;
R
1=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
2=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
3=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
4=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon;
R
5=hydrogen, fluorine, chlorine, bromine, iodine, trifluoromethyl, the alkoxyl group of the alkyl of 1-8 carbon or 1-8 carbon.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702261A (en) * | 2012-05-29 | 2012-10-03 | 南京信息工程大学 | Method for preparing 1-substituted phenyl-4-ethoxycarbonyl-5-(diphenylphosphinyl)amino-1, 2, 3-triazole |
| CN103524557A (en) * | 2009-09-02 | 2014-01-22 | 上海交通大学 | 5,5'-connected 1,1'-biphenyl axially chiral 2,2'-diphosphine ligand and preparation method thereof |
-
2007
- 2007-11-22 CN CNA2007101707749A patent/CN101168549A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524557A (en) * | 2009-09-02 | 2014-01-22 | 上海交通大学 | 5,5'-connected 1,1'-biphenyl axially chiral 2,2'-diphosphine ligand and preparation method thereof |
| CN103524557B (en) * | 2009-09-02 | 2016-08-10 | 上海交通大学 | 1,1`-diphenyl axially chiral 2,2 '-biphosphine ligand that 5,5` position connects and preparation method thereof |
| CN102702261A (en) * | 2012-05-29 | 2012-10-03 | 南京信息工程大学 | Method for preparing 1-substituted phenyl-4-ethoxycarbonyl-5-(diphenylphosphinyl)amino-1, 2, 3-triazole |
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