CN1775789A - Method for synthesizing di-ferrocene phosphine diimine structure connected with aliphatic series and benzene ring - Google Patents
Method for synthesizing di-ferrocene phosphine diimine structure connected with aliphatic series and benzene ring Download PDFInfo
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Abstract
The invention relates to a method for synthesizing planar chiral diferrocene phosphine diimide, and this ligand contains diimine and has a planar chiral diferrocene structure. This compound is condensed of planar chiral ferroceneprimary amide and various dialdehyde compounds under the existence of shrinking agent. The dialdehyde compounds can be p-phthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, phenyl dialdehyde, butyl dialdehyde, glutaric dialdehyde, etc. and the method has the advantages of simple synthesizing route, simple operation, easy purification, and high yield. The invention is applied to the catalytic reactions such as aromatic ketone unsymmetrical hydrogen transfer reaction and can achieve very high yield and enantiotropic selectivity.
Description
Background
The ferrocene catalyst ligand has high catalytic activity and high enantioselectivity in many reactions, and the common ferrocene catalyst ligand is mostly a mono-ferrocene derivative, and the compounds are easily dissolved in most organic solvents and are difficult to extract and separate after catalytic reaction, so that a large amount of expensive chiral ligands are difficult to recycle, and the application of the ferrocene derivative in industrial asymmetric catalysis is greatly hindered. The chiral biferrocenyl phosphine diimine ligands are important ligands, and the ligands not only have the bidentate ability, but also have the reduced polarity of the biferrocenyl structure, thereby being beneficial to realizing the recycling by utilizing the solubility difference.
Daiki et al studied and synthesized a planar chiral biferrocene Schiff base imine structure (molecular formula shown below), and applied the ligand to Ru (II) catalyzed asymmetric cyclopropanation (molecular catalysis, 2004, 1-5). However, for asymmetric cyclopropanation the enantioselective effect of the ligand is not very good, the best ee is only 65%.
R＝H，CH3
Asymmetric hydrogen transfer reactions, which are an effective reduction method, catalytically reduce C ═ O double bonds using non-toxic organic molecules as the hydrogen source, have the advantage of simple operation, do not require the use of highly active metal hydrides and hydrogen, and are distinguished from hydrogen catalytic reduction in selectivity. If a suitable catalyst is selected, ketones having a latent chirality can be reduced to chiral secondary alcohols having high optical activity, and thus ligands having high selectivity have been the hot spot of many chemists.
Disclosure of Invention
The invention designs and synthesizes a biferrocenyl phosphine diimine ligand with planar chirality. Due to the specific rigid C ═ N bond, the aromatic ring and the flexible alkyl chain, the planar chiral biferrocenyl phosphine diimine can form various three-dimensional microenvironments in various asymmetric catalytic reactions, and the ligand can obtain good enantioselectivity when being applied to the asymmetric hydrogen transfer reaction of catalytic ketone. In addition, the specific bis-metallocene structure reduces the polarity of ferrocene derivatives, so that the solubility of the ferrocene derivatives in certain solvents can be reduced, and the ligand can be separated from a reaction system by utilizing the difference of the solubility after the catalytic reaction is finished, thereby achieving the purpose of catalyst recovery.
The invention provides a novel planar chiral ferrocene phosphine diimine ligand, wherein a molecular general formula of the ligand is a structure R for connecting two planar chiral ferrocene, namely a dialdehyde compound reacted with chiral ferrocenylamine can be terephthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, malondialdehyde, succindialdehyde, glutaraldehyde and hexandialdehyde.
R＝CH2，(CH2)2，(CH2)3，(CH2)4，(CH2)5，
The invention also aims to provide a corresponding method for preparing the compound, namely, under the reflux temperature of an organic solvent, the compound is obtained by condensing primary ferrocene with planar chirality and various dialdehyde compounds in the presence of a shrinking agent, and the reaction formula is as follows:
the invention also provides the application of the target compound, namely the bisferrocenyl phosphine diimine ligand. A large number of experimental researches show that the synthesized novel planar chiral bis-ferrocenyl phosphine diimine is applied to the asymmetric hydrogen transfer reaction of aromatic ketones such as indole, bi-aromatic ketones and condensed ring aromatic ketones, and good enantioselectivity is obtained. The synthesized ligand is applied to iridium-catalyzed asymmetric hydrogenation reaction, and the substrate structure suitable for the ligand is as follows:
R3＝CnH2n+1
R4＝CnH2n+1
compared with the prior art, the ligand and the application thereof provided by the invention have the characteristics of good yield and enantioselectivity. And because they have biferrocenyl, they have very high catalytic activity and chiral induction effect in iridium-catalyzed asymmetric hydrogenation reactions, and in addition, the ligand is applied to ruthenium, rhodium and other metal-catalyzed asymmetric hydrogen transfer reactions in research. The ligand has better application prospect in asymmetric hydrogenation and asymmetric hydrogen transfer reaction.
The attached drawings of the specification:
FIG. 1: a synthetic diagram of planar chiral ferrocene phosphinimine;
examples
The present invention is further illustrated by the following examples, but is not limited to the following examples.
Example 1
(R) -N, N-dimethyl-1-ferrocenylethylamine (synthesis and resolution of racemate carried out according to the method reported by D.Marquarding et al) is dissolved in anhydrous ether, lithiated with N-butyllithium and quenched with diphenylphosphine chloride to obtain [ (R, S)p)-2]. Will [ R, S]p)-2]Dissolving in anhydrous acetic anhydride, reacting at 100 ℃ for 2h to precipitate a crystal 3. And dissolving the crystal 3 in methanol, adding excessive ammonia water, and reacting at 80 ℃ for 7h to obtain ferrocenyl primary amine 4. Dissolving ferrocenyl phosphamide compound 4(868mg, 2.1mmol) and glutaraldehyde (395mg, 4.2mmol) in absolute ethanol, adding molecular sieve (5g) and refluxing for 4 hours, evaporating ethanol under reduced pressure to obtain red solid, washing with hot water to remove unreacted excessive glutaraldehyde (10ml × 2), drying to obtain crude product 5, dissolving 5 in ethanol, adding ferrocenyl phosphamide compound 4(868mg, 2.1mmol) and refluxing for 2 hours to obtain precipitate, after the reaction is finished, extracting solvent under reduced pressure to obtain yellow solid, and recrystallizing the crude product in dichloromethane/petroleum ether to obtain red crystal 6(0.68g, 86%).
mp 248-250℃([α]D 2+543.9(c 0.4，CH2Cl2) An infrared spectrum (IR) showing an unsubstituted cyclopentadienyl ring (1103.9 and 996.6cm-1), 1022.0 ℃; E1147.6cm-1 (substituted cyclopentadienyl ring), 486.1cm-1 and509.9cm-1 (v)Fe-C)，1621 and 1639cm-1(N＝CH)；1H NMR(CDCl3)δH：(ppm)0.72(d，J＝6.7，6H，CHCH3)，4.10(s，10H，Fc-unsubst.Ring)，4.06-4.22(m，8H，FeC5H3CH)，7.22-7.60(m，40H，C6H5)，8.06(s，4H，C6H4)，8.31(s，1H，N＝CH)，8.84(s，1H，N＝CH)；
Example 2
The conditions were the same as in example 1 except that terephthalaldehyde was changed to m-phthalaldehyde.
Example 3
The conditions were the same as in example 1 except that terephthalaldehyde was changed to o-phthalaldehyde.
Example 4
The conditions were the same as in example 1 except that terephthalaldehyde was changed to malonaldehyde.
Example 5
The conditions were the same as in example 1 except that terephthalaldehyde was changed to succinaldehyde.
Example 6
The conditions were the same as in example 1 except that terephthalaldehyde was changed to glutaraldehyde.
Example 7
The conditions were the same as in example 1 except that terephthalaldehyde was changed to adipic dialdehyde.
Example 8
1 mmol% of [ Ir (COD) Cl]21 mmol% of the ligand from example 6 to 8mL of anhydrous isopropanol, N2Reacting for 1h at 80 ℃ under protection. Cooled to room temperature, 3 mmol% KOH was added and 2mmol 4-benzoylpyridine was added. Reacting at 30-50 deg.C. TLC monitored the progress of the reaction. After the reaction is finished, the solvent is removed under reduced pressure, and the product is obtained by column chromatography separation (silica gel 100-mesh, 4-benzoylpyridine, ethyl acetate). HPLC analysis (chiral OD column), mobile phase: n-hexane and isopropanol are 80: 20, and the ee percent of the product is more than 99 percent.
Claims (2)
1. A synthetic method of a biferrocenyl phosphine diimine structure connected by aliphatic series and benzene rings is characterized in that: the structure R connecting two planar chiral ferrocenes in the molecular general formula, namely the dialdehyde compound reacted with the chiral ferrocenylamine can be terephthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, malonaldehyde, succinaldehyde, glutaraldehyde and adipaldehyde.
R＝CH2，(CH2)2，(CH2)3，(CH2)4，(CH2)5，
2. The method for synthesizing a biferrocenyl phosphinimine structure connected by an aliphatic group and a benzene ring according to claim 1, wherein the method comprises the following steps: the synthesized ligand is applied to iridium-catalyzed asymmetric hydrogenation reaction, and the substrate structure suitable for the ligand is as follows:
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486737B (en) * | 2009-03-06 | 2011-06-01 | 北京理工大学 | Ferrocene phosphinimine ligand containing quaternary ammonium salt group, preparation thereof and use for catalyzing asymmetric allyl group substitution reaction |
| CN101712697B (en) * | 2008-10-07 | 2011-09-07 | 北京理工大学 | Ferrocene phosphinimine ligand containing imidazole salt group, preparation thereof and application in catalyzing asymmetric allyl substitution reaction |
| CN101570550B (en) * | 2009-06-09 | 2012-03-07 | 武汉理工大学 | Method for synthesizing chiral ferrocene diphosphine ligand |
| CN103242377A (en) * | 2013-04-22 | 2013-08-14 | 苏州志向纺织科研股份有限公司 | Alpha,omega-biferrocene hydrocarbon and preparation method thereof |
| CN108620129A (en) * | 2018-05-24 | 2018-10-09 | 江西师范大学 | Spherical Fc- (COOH)2@COFETTA-TPALThe preparation method of nanocomposite |
-
2005
- 2005-11-18 CN CNB2005101148505A patent/CN100537582C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712697B (en) * | 2008-10-07 | 2011-09-07 | 北京理工大学 | Ferrocene phosphinimine ligand containing imidazole salt group, preparation thereof and application in catalyzing asymmetric allyl substitution reaction |
| CN101486737B (en) * | 2009-03-06 | 2011-06-01 | 北京理工大学 | Ferrocene phosphinimine ligand containing quaternary ammonium salt group, preparation thereof and use for catalyzing asymmetric allyl group substitution reaction |
| CN101570550B (en) * | 2009-06-09 | 2012-03-07 | 武汉理工大学 | Method for synthesizing chiral ferrocene diphosphine ligand |
| CN103242377A (en) * | 2013-04-22 | 2013-08-14 | 苏州志向纺织科研股份有限公司 | Alpha,omega-biferrocene hydrocarbon and preparation method thereof |
| CN103242377B (en) * | 2013-04-22 | 2016-02-10 | 苏州志向纺织科研股份有限公司 | A kind of α, ω-di-ferrocene hydrocarbon and preparation method thereof |
| CN108620129A (en) * | 2018-05-24 | 2018-10-09 | 江西师范大学 | Spherical Fc- (COOH)2@COFETTA-TPALThe preparation method of nanocomposite |
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