CN105753906A - Chiral bidentate phosphite ligand derived from cyclohexanediol and preparation method and application of ligand - Google Patents
Chiral bidentate phosphite ligand derived from cyclohexanediol and preparation method and application of ligand Download PDFInfo
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- CN105753906A CN105753906A CN201410785924.7A CN201410785924A CN105753906A CN 105753906 A CN105753906 A CN 105753906A CN 201410785924 A CN201410785924 A CN 201410785924A CN 105753906 A CN105753906 A CN 105753906A
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- cyclohexanediol
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Abstract
The invention discloses a chiral bidentate phosphite ligand derived from cyclohexanediol, a preparation method of the ligand, and an application of the ligand to an asymmetric 1,4-conjugate addition reaction of an organic zinc reagent and cyclic ketenes. The ligand has a general structural formula shown in the description. In the general structural formula, R has any one of structural formulas shown in the description. The ligand together with a copper complex has high catalytic activity and optical selectivity for the 1,4-conjugate addition reaction of cyclic ketenes. The method has advantages of simple synthetic route, low preparation cost, and stability of the ligand in air.
Description
Technical field
The present invention relates to derivative chiral bidentate phosphite ligand of a kind of cyclohexanediol and its preparation method and application.Part/Cu complex as the catalyst organic zinc reagent asymmetric Isosorbide-5-Nitrae-conjugate addition reaction to ring-type ketenes, is obtained having optically active beta substitution cyclic ketone by the present invention.
Background technology
Alkyl or aryl zincon is to α, and the Isosorbide-5-Nitrae-conjugate addition of beta-unsaturated carbonyl compound is one of the important reaction forming C-C key, and asymmetric Isosorbide-5-Nitrae-conjugate addition reaction can synthesize the medicine or intermediate with physiologically active, as muscone ((R)-Muscone), mycobacteria reagent (erogorgiaene), anticancer class medicine (ClavularinB), cardiovascular disease therapies medicine (PGE1), noncompetitive blockers ((-)-pumiliotoxinC) and ibuprofen [(+)-ibuprofen].Therefore, in recent years, this reaction receives significant attention and furthers investigate.
Design synthesis can form the chiral ligand of complex compound catalyst with metal, is the key realizing efficient asymmetric Isosorbide-5-Nitrae-conjugate addition reaction.1993, the ligand complex catalyzed asymmetric Isosorbide-5-Nitrae of Alexakis reported first copper-phosphorus (III)-conjugate addition reaction [Alexakis, A.;Frutos,J.;Mangeney,P.Tetrahedron:Asymmetry1993,4,2427-2430].Since then, many chiral phosphorus ligand (such as: chiral phosphoramidite ester part, chirality phosphite ester ligand, chirality P, O and P, N part etc.) are successfully applied in this reaction [PerezHF, EtayoP, PanossianA, FerranAV.Chem.Rev.2011,111,3,2119-2176].These parts have had more than one piece patent application publication, such as US20070259774A1, US20090124836A1, US7728177B2, EP1884509A1, CN101565436A, CN101090904A.
At present, multiple α, β-unsaturated ketenes substrate is not all had high asymmetric induction ability by existing outstanding chiral ligand；And this reaction generally requires specific reaction condition and just can provide higher enantioselectivity.Therefore, design synthesis of chiral phosphorus part and the applied research in Isosorbide-5-Nitrae-conjugate addition reaction are still significant.
Summary of the invention
It is an object of the invention to provide derivative chiral bidentate phosphite ligand of a kind of cyclohexanediol and its preparation method and application.
The chiral bidentate phosphite ligand that cyclohexanediol is derivative, is structured with formula:
Wherein R is any one in following structural formula:
The preparation method of the chiral bidentate phosphite ligand that cyclohexanediol is derivative is as follows:
Under normal pressure nitrogen atmosphere, in oxolane (THF) solvent, with anti-form-1,2-cyclohexanediol,R-orSPhosphorous acyl chlorides, DMAP (DMAP) and the triethylamine (NEt that-dinaphthol derives3) for reactant, react 1-2 hour at-15 ~ 0 DEG C, then removal of solvent under reduced pressure, add toluene, after being sufficiently stirred for, elimination insoluble matter, filtrate concentrates, and through column chromatography for separation, obtains the chiral bidentate phosphite ligand that cyclohexanediol is derivative.
Described anti-form-1,2-cyclohexanediol withR-orSThe mol ratio of the phosphorous acyl chlorides that-dinaphthol is derivative is 1:2 ~ 3.
Described DMAP and anti-form-1, the mol ratio of 2-cyclohexanediol is 1:4 ~ 5.
The mol ratio of described anti-form-1,2-cyclohexanediol and triethylamine is 1:3 ~ 4.
Chiral bidentate phosphite ligand and metallic copper precursor reaction in-situ that described cyclohexanediol is derivative prepare catalyst, and the catalysis organic zinc asymmetric Isosorbide-5-Nitrae-conjugate addition reaction to ring-type ketenes obtains having optically active beta substitution cyclic ketone product.
Illustrate organic zinc the asymmetric 1,4-conjugate addition reaction process of ring-type ketenes is as follows:
Under normal pressure nitrogen atmosphere, in organic solvent, described part and Cu salt reaction in-situ one hour, prepare part-Cu catalyst.Then it is sequentially added into ring-type ketenes and organic zinc wherein, reacts 4 ~ 12 hours at-40 ~ 20 DEG C, then add distilled water and dilute hydrochloric acid solution cancellation reaction in the reactive mixture, be extracted with ethyl acetate, merge organic facies, use saturated NaHCO successively3Solution, saturated common salt water washing, anhydrous Na2SO4Dry, to filter, concentration, synthesis has optically active beta substitution cyclic ketone product, gas chromatogram (GC) assay products.
Described Cu salt is selected from copper trifluoromethanesulfcomposite [Cu (OTf)2], the cuprous benzene complex of trifluoromethanesulfonic acid [(CuOTf)2·C6H6] or Cu (OAc)2·H2O, wherein OTf is trifluoromethanesulfonic acid base；The mol ratio of Cu salt and part is 1:2 ~ 2:1；Organic zinc reagent is selected from zinc methide, diethyl zinc or diphenyl zinc；Organic solvent is selected from oxolane, ether, toluene or dichloromethane.
Described ring-type ketenes is selected from 2-cyclopentenone, 2-cyclonene or 2-cycloheptene ketone；The mol ratio of part/Cu catalyst, ring-type ketenes and organic zinc is 1:50:120.
The anti-form-1 that the present invention is previously mentioned, 2-cyclohexanediol low price, and in atmosphere can stable existence, its chemical modification is easily carried out；Chirality phosphite ester ligand has the features such as synthetic route is simple, cost is low, stable in the air, and the Isosorbide-5-Nitrae-conjugate addition reaction of ring-type ketenes is had high catalysis activity and optical selective by its metallic copper complex.Apply this chiral ligand, the medicine or intermediate with physiologically active can be prepared by asymmetric Isosorbide-5-Nitrae-conjugate addition reaction, in the industries such as medicine, pesticide, spice and natural chiral Product formation, there is important using value.
Detailed description of the invention
Embodiment 1 prepares chirality phosphite ester ligand, and structural formula is as follows:
Under normal pressure nitrogen atmosphere, to equipped with, in the 100mL Xiu Langke bottle of magneton, adding anti-form-1,2-cyclohexanediol (87.5mg, 0.75mmol), phosphorous acyl chlorides (529.3mg, 1.51mmol) with DMAP (18.4mg, 0.15mmol), add 10mL oxolane and make solvent, stirring makes solid be completely dissolved, solution is cooled to-15 DEG C, is slowly added dropwise triethylamine 0.32mL, at-15-0 DEG C, react 1h.Removal of solvent under reduced pressure, adds 20mL toluene and is sufficiently stirred for, filter solid, after filtrate being concentrated, obtains ligand 1 69.3mg through flash of light chromatographic isolation, and yield is 30.34%.
White foam solid.31PNMR(161MHz,CDCl3):δ148.27;1HNMR(400MHz,CDCl3):δ7.97-7.85(m,6H),7.81(d,J=8.8Hz,1H),7.72(d,J=8.8Hz,1H),7.50(t,J=8.4Hz,2H),7.46-7.33(m,10H),7.29-7.20(m,4H),4.31-4.08(m,2H),2.28-2.12(m,1H),2.08-1.90(m,2H),1.74-1.43(m,5H);13CNMR(100MHz,CDCl3): δ 151.74,132.46,130.28,129.21,128.42,126.37,126.03,123.25,122.93,117.77,66.94,30.56,24.58.
Embodiment 2 prepares chirality phosphite ester ligand, and structural formula is as follows:
With the method in embodiment 1, anti-form-1,2-cyclohexanediol (62.3mg, 0.54mmol), phosphorous acyl chlorides (412.7mg, 1.18mmol) and DMAP (14.4mg, 0.12mmol), triethylamine 0.25mL, 2 hours response time.All the other are with embodiment 1, obtain part 320.1mg, yield 79.65%.
White foam solid.31PNMR(161MHz,CDCl3):δ148.35;1HNMR(400MHz,CDCl3):δ7.95-7.87(m,6H),7.80(d,J=8.8Hz,1H),7.71(d,J=8.8Hz,1H),7.51(dd,J=8.8,6.0Hz,2H),7.38(dd,J=18.8,9.6Hz,10H),7.22(d,J=4.0Hz,4H),4.20(d,J=55.8Hz,2H),2.18(d,J=12.4Hz,1H),1.97(d,J=12.8Hz,1H),1.56(dd,J=54.0,18.8Hz,6H);13CNMR(100MHz,CDCl3):δ151.74,131.81,130.51,129.21,128.70,127.29,126.04,123.72,123.20,116.74,66.95,30.57,28.68.
Embodiment 3 prepares chirality phosphite ester ligand, and structural formula is as follows:
With the method in embodiment 1, anti-form-1,2-cyclohexanediol (77.9mg, 0.67mmol), phosphorous acyl chlorides (530.0mg, 1.48mmol) and DMAP (18.0mg, 0.15mmol), triethylamine 0.26mL, 1 hour response time.All the other are with embodiment 1, obtain ligand 1 24.0mg, yield 24.34%.
White foam solid.31PNMR(161MHz,CDCl3):δ128.77;1HNMR(400MHz,CDCl3):δ7.08-6.89(m,7H),6.85-6.79(m,1H),4.17(d,J=52.6Hz,2H),2.85-2.57(m,12H),2.31-2.20(m,4H),1.84-1.44(m,24H);13CNMR(100MHz,CDCl3):δ145.62,136.38,133.48,128.02,127.21,117.88,28.68,28.18,26.72,21.72,21.65,21.53,21.46.
Embodiment 4 prepares chirality phosphite ester ligand, and structural formula is as follows:
With the method in embodiment 1, anti-form-1,2-cyclohexanediol (64.9mg, 0.56mmol), phosphorous acyl chlorides (500.0mg, 1.40mmol) and DMAP (17.1mg, 0.14mmol), triethylamine 0.26mL, 2 hours response time.All the other are with embodiment 1, obtain ligand 1 32.7mg, yield 31.16%.
White foam solid.31PNMR(161MHz,CDCl3):δ128.65;1HNMR(400MHz,CDCl3):δ7.03-6.83(m,7H),6.79-6.71(m,1H),4.10(d,J=52.6Hz,2H),2.82-2.51(m,12H),2.24-2.10(m,4H),1.77-1.37(m,24H);13CNMR(100MHz,CDCl3):δ144.90,136.70,133.22,128.00,127.19,117.94,28.15,28.13,26.73,21.62,21.59,21.49,21.41.
Embodiment 5
In a nitrogen atmosphere, Cu (OTf)2Part (0.005mmol, 3.7mg) described in (0.005mmol, 1.8mg) and embodiment 1 is dissolved in 4mL toluene, 1h is stirred at room temperature, obtains the solution of part-Cu catalyst.It is cooled to 0 DEG C, is sequentially added into 2-cyclonene (0.25mmol, 25 μ L), diethyl zinc (hexane solution of 1mol/L, 0.6mL), reacts 4 hours at 0 DEG C.Add 2mL distilled water and 2mL dilute hydrochloric acid solution (2.0mol/L) cancellation reaction, be extracted with ethyl acetate (5mL × 3), merge organic facies, use saturated NaHCO successively3Solution, saturated common salt water washing, anhydrous Na2SO4Dry, filter, concentration, analyze through gas chromatogram (GC), 2-cyclonene conversion ratio is 66%, and product enantioselectivity is 42%, and absolute configuration isR。
Embodiment 6
With embodiment 5, part is selected from the part (0.005mmol, 3.7mg) described in embodiment 2, and GC analyzes display, and 2-cyclonene conversion ratio is 45%, and product enantioselectivity is 17%, and absolute configuration isS。
Embodiment 7
With embodiment 5, part is selected from the part (0.005mmol, 3.8mg) described in embodiment 3, and GC analyzes display, and 2-cyclonene conversion ratio is 99%, and product enantioselectivity is 12%, and absolute configuration isR。
Embodiment 8
With embodiment 5, part is selected from the part (0.005mmol, 3.8mg) described in embodiment 4, and GC analyzes display, and 2-cyclonene conversion ratio is 60%, and product enantioselectivity is 15%, and absolute configuration isS。
Embodiment 9
With embodiment 5, solvent analyzes display selected from ether 4mL, GC, and 2-cyclonene conversion ratio is 99%, and product enantioselectivity is 52%, and absolute configuration isR。
Embodiment 10
With embodiment 5, solvent analyzes display selected from dichloromethane 4mL, GC, and 2-cyclonene conversion ratio is 91%, and product enantioselectivity is 37%, and absolute configuration isR。
Embodiment 11
With embodiment 5, solvent analyzes display selected from oxolane 4mL, GC, and 2-cyclonene conversion ratio is 68%, and product enantioselectivity is 42%, and absolute configuration isR。
Embodiment 12
With embodiment 5, mantoquita is selected from Cu (OAc)2·H2O (0.005mmol, 1.0mg), GC analyze display, and 2-cyclonene conversion ratio is 80%, and product enantioselectivity is 12%, and absolute configuration isR。
Embodiment 13
With embodiment 5, mantoquita is selected from (CuOTf)2·C6H6(0.0025mmol, 1.25mg), GC analyzes display, and 2-cyclonene conversion ratio is 50%, and product enantioselectivity is 98%, and absolute configuration isR。
Embodiment 14
With embodiment 5, reaction temperature is 20oC, GC analyze display, and 2-cyclonene conversion ratio is 92%, and product enantioselectivity is 91%, and absolute configuration isR。
Embodiment 15
With embodiment 5, reaction temperature is-10oC, the response time is 12 hours, and GC analyzes display, and 2-cyclonene conversion ratio is 89%, and product enantioselectivity is 84%, and absolute configuration isR。
Embodiment 16
With embodiment 5, reaction temperature is-20oC, the response time is 12 hours, and GC analyzes display, and 2-cyclonene conversion ratio is 83%, and product enantioselectivity is 83%, and absolute configuration isR。
Embodiment 17
With embodiment 5, reaction temperature is-30oC, the response time is 12 hours, and GC analyzes display, and 2-cyclonene conversion ratio is 35%, and product enantioselectivity is 85%, and absolute configuration isR。
Embodiment 18
With embodiment 5, reaction temperature is-40oC, the response time is 12 hours, and GC analyzes display, and 2-cyclonene conversion ratio is 19%, and product enantioselectivity is 46%, and absolute configuration isR。
Embodiment 19
With embodiment 5, part consumption (0.0025mmol, 1.9mg) as described in Example 1, GC analyzes display, and 2-cyclonene conversion ratio is 70%, and product enantioselectivity is 95%, and absolute configuration isR。
Embodiment 20
With embodiment 5, part consumption (0.01mmol, 7.4mg) as described in Example 1, GC analyzes display, and 2-cyclonene conversion ratio is 39%, and product enantioselectivity is 92%, and absolute configuration isR。
Embodiment 21
With embodiment 5, organic zinc reagent is selected from zinc methide (1.20mmol, 1.0mL).GC analyzes display, and 2-cyclonene conversion ratio is 29%, and product enantioselectivity is 47%, and absolute configuration isR。
Embodiment 22
With embodiment 5, organic zinc reagent is selected from diphenyl zinc (0.60mmol, 131.7mg).GC analyzes display, and 2-cyclonene conversion ratio is 70%, and product enantioselectivity is 64%, and absolute configuration isR。
Embodiment 23
With embodiment 5, annulenones substrate is selected from 2-cyclopentenone (0.25mmol, 0.022mL).GC analyzes display, and 2-cyclopentenone conversion ratio is 79%, and product enantioselectivity is 54%, and absolute configuration isR。
Embodiment 24
With embodiment 5, annulenones substrate is selected from 2-cycloheptene ketone (0.25mmol, 0.030mL).GC analyzes display, and 2-cycloheptene ketone conversion ratio is 22%, and product enantioselectivity is 43%, and absolute configuration isR。
Claims (6)
1. the chiral bidentate phosphite ligand that cyclohexanediol is derivative, it is characterised in that the general structure of this part is as follows:
Wherein R is any one in following structural formula:
。
2. the preparation method of part as claimed in claim 1, it is characterised in that specifically comprise the following steps that
Under normal pressure nitrogen atmosphere, in tetrahydrofuran solvent, with anti-form-1,2-cyclohexanediol,R-orSPhosphorous acyl chlorides, DMAP and triethylamine that-dinaphthol derives are reactant, react 1-2 hour at-15 ~ 0 DEG C, then removal of solvent under reduced pressure, add toluene, after being sufficiently stirred for, elimination insoluble matter, filtrate concentrates, through column chromatography for separation, obtain the chiral bidentate phosphite ligand that cyclohexanediol is derivative.
3. preparation method as claimed in claim 2, it is characterised in that described anti-form-1,2-cyclohexanediol withR-orSThe mol ratio of the phosphorous acyl chlorides that-dinaphthol is derivative is 1:2 ~ 3.
4. preparation method as claimed in claim 2, it is characterised in that described DMAP and anti-form-1, the mol ratio of 2-cyclohexanediol is 1:4 ~ 5.
5. preparation method as claimed in claim 2, it is characterised in that the mol ratio of described anti-form-1,2-cyclohexanediol and triethylamine is 1:3 ~ 4.
6. part application in the organic zinc reagent asymmetric 1,4-conjugate addition reaction with ring-type ketenes as claimed in claim 1.
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| US20060224002A1 (en) * | 2003-11-12 | 2006-10-05 | Studiengesellschaft Kohle Mbh | Chiral di- and triphosphites |
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| CN102532225A (en) * | 2010-12-23 | 2012-07-04 | 中国科学院兰州化学物理研究所 | Chiral phosphate ester ligand derived from methyl glucoside as well as preparation method and application thereof |
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2014
- 2014-12-18 CN CN201410785924.7A patent/CN105753906A/en active Pending
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| CN1169143A (en) * | 1995-01-27 | 1997-12-31 | 纳幕尔杜邦公司 | Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles |
| US20060224002A1 (en) * | 2003-11-12 | 2006-10-05 | Studiengesellschaft Kohle Mbh | Chiral di- and triphosphites |
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