CN109232650B - Chiral 1-phospha norbornadiene derivative and synthesis method thereof - Google Patents
Chiral 1-phospha norbornadiene derivative and synthesis method thereof Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- OIFRCRAYWOPACM-UHFFFAOYSA-N 1-phosphabicyclo[2.2.1]hepta-2,4-diene Chemical class C1P2CC=C1C=C2 OIFRCRAYWOPACM-UHFFFAOYSA-N 0.000 title abstract description 4
- -1 1-phospha norbornadiene compound Chemical class 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- DJMUYABFXCIYSC-UHFFFAOYSA-N 1H-phosphole Chemical compound C=1C=CPC=1 DJMUYABFXCIYSC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011574 phosphorus Substances 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 76
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 238000004679 31P NMR spectroscopy Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- CTJCNGICLXYWOR-UHFFFAOYSA-N 2H-phosphole Chemical compound C1C=CC=P1 CTJCNGICLXYWOR-UHFFFAOYSA-N 0.000 description 1
- IDASOVSVRKONFS-UHFFFAOYSA-N 3-phenylprop-2-ynal Chemical compound O=CC#CC1=CC=CC=C1 IDASOVSVRKONFS-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 238000004296 chiral HPLC Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011981 development test Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical compound C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- LFILDSDQMSCNBV-LURJTMIESA-N propane-2-sulfinamide Chemical compound CC(C)[S@@](N)=O LFILDSDQMSCNBV-LURJTMIESA-N 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention belongs to the field of organic chemical synthesis, and particularly relates to a 1-phospha norbornadiene compound with application value in the field of asymmetric catalysis and a synthesis method thereof. Synthesizes a series of chiral phosphine ligands of phosphorus chiral center, combines 1-phospha norbornadiene skeleton and chiral sulfoxide compounds, and has wide application prospect in the field of asymmetric catalysis. It has the following structural general formula:
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a 1-phospha norbornadiene compound applied to the field of asymmetric catalysis and a synthesis method thereof.
Background
In the field of asymmetric catalysis, chiral organophosphates are important ligands or catalysts. Because of possessing a pair of lone pair electrons, the trivalent organic phosphide can be used as a ligand to be complexed with metal to generate a metal complex to participate in metal-catalyzed asymmetric reaction, and can also be used as a catalyst to attack electron-deficient olefin to generate a carbanion intermediate to catalyze chemical reaction. In previous studies, chemists focused their attention on the selection of chiral backbones linked to phosphorus, i.e., the chirality of the target product was generated by the induction of the chiral backbone. Phosphorus chiral center ligands have been studied very rarely because of the difficulty in synthesis of phosphorus chiral centers and the susceptibility to racemization at high temperatures due to the nature of phosphorus.
To date, the design of chiral phosphorus-oxygen ligands with a phosphorus chiral center by the incorporation of phosphorus atoms into rigid backbones has not been reported.
Disclosure of Invention
Aiming at the current technical situation, the invention aims to provide a novel 1-phospha norbornadiene chiral phosphorus-oxygen ligand; another object is to provide a method for synthesizing the same.
In order to realize the purpose of the invention, the invention takes phospholane diene compound as an initiator to generate the 1-phospholane norbornadiene compound through a phospholane D-A reaction. The general formula is as follows:
ar is phenyl, naphthyl, phenyl substituted by C1-5 alkyl or C1-5 alkoxy.
Preferably: ar is phenyl, naphthyl, phenyl substituted by methyl, butyl or methoxy or butoxy.
The scheme route is as follows:
(1) in N2Under the environment, toluene, phosphole A1 and compound A2 are added into a Schlenk bottle and reacted in oil bath at 130-140 ℃. And (5) passing through a column to obtain the compound A3.
(2) In N2Dichloromethane, compound a3, hydrochloric acid, silica were added to a Schlenk flask under ambient conditions and the reaction was stirred at room temperature. After the reaction is completed, H is used2And washing, drying and spin-drying to obtain the compound A4.
(3) In N2Tetrahydrofuran, compound A4, R-tert-butylimine sulfonate and titanium tetraisopropoxide are added into a Schlenk bottle under the environment, and oil bath reaction is carried out at 40-50 ℃. Extracting, drying and separating by column chromatography to obtain compound A5.
(4) A method for synthesizing compounds II-a to II' -g comprises the following steps:
respectively putting the compound A5 in a Schlenk bottle, vacuumizing, filling nitrogen, adding tetrahydrofuran, adding an aryl lithium reagent at the temperature of between 70 ℃ below zero and 78 ℃ below zero, continuing the reaction at the temperature, and adding NH into the reaction system when the reaction is complete4And (3) extracting with Cl solution, combining organic layers, drying, filtering, evaporating the solvent under reduced pressure, and carrying out column chromatography separation to obtain corresponding products II and II'.
The following compounds are obtained:
the invention has the advantages that: 1. the synthesis method is simple and feasible, and the yield is higher and reaches more than 61 percent; 2. the target object II is taken as a phosphorus chiral center ligand with a novel structure, the scientific problem that the phosphorus chiral center is easy to racemize is successfully solved by introducing a rigid framework, and the phosphorus chiral center ligand is an effective chiral ligand, can be widely applied to asymmetric reaction in the future and has wide commercial application prospect.
Detailed Description
To better illustrate the invention, the following examples are given:
example 1
(1) In N2Under the environment, 40mL of methanol, phenylpropargylaldehyde (20mmol) and trimethyl orthoformate (40mmol) are added into a 100mLSchlenk bottle, then catalyst p-toluenesulfonic acid (10 mol%) is added, and the mixture is transferred into a 65 ℃ oil bath and refluxed for 10 hours. After the reaction is completed, a small amount of NaOH solid is added, and the stirring is continued for 20 min. After reduced pressure rotary evaporation, the mixture is passed through a neutral alumina dry column and is dried by spinning to obtain a compound A2 with the yield of 93 percent.
(2) In N2At ambient temperature, 5mL of toluene, Compound A2(5.6mmol), phospha-cyclopentadiene (5.3mmol) were added to a 75mL Schlenk bottle. The reaction was carried out in an oil bath at 140 ℃ for 2 h. Passing through a neutral alumina column (PE: DCM ═ 10:1) affords compound a 3. The yield was 80%.
(3) In N2To a 100mL Schlenk flask, 20mL of dichloromethane, Compound A3, hydrochloric acid, and silica were added and stirred at room temperature for 3 h. After the reaction is completed, H is used2O Wash (20mL x 3), MgSO4And (5) drying. The compound A4 was obtained in 86% yield by spin-drying.
1H NMR(CDCl3):d(ppm)-1.4(s,3H),2.1(s,3H),2.2(m,2H),6.8–7.3(m,10H),9.7(d,J-9.2Hz,1H)ppm；13C NMR(CDCl3):d(ppm)-16.5,20.4,65.1,73.6(d,J-5.9Hz),191.0(d,J-16.7Hz)ppm；31P NMR(CDCl3)d(ppm)--31.2ppm.
(4) In N240mL of THF, Compound A4(7.4mmol), R-t-butylsulfonimide (8mmol), and titanium tetraisopropoxide (16mmol) were added to a 100mL Schlenk flask and reacted in an oil bath at 50 ℃ for 3 h. Extracted with ethyl acetate (100 mL. times.3), MgSO 24And (5) drying. And (DCM: EA: 1). Compound a5 was obtained in 61% yield.
(4) A method for synthesizing compounds II-a to II' -g comprises the following steps:
respectively putting a compound raw material A5 into a Schlenk bottle, vacuumizing, charging nitrogen, adding tetrahydrofuran, adding 2.0 equivalent of different aryl lithium reagents at-78 ℃, continuing to react for 10 hours at the temperature, and adding NH into the reaction system when the reaction is complete4Cl solution, then extracted with ethyl acetate, the organic layers were combined and MgSO4Drying, filtering, vacuum evaporating to remove solvent, and separating by column chromatography. Corresponding products II-a to II' -g are obtained.
(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(phenyl)methyl)-2-methylpropane-2-sulfinamide
35％yield；yellow solid
31P NMR(121MHz,CDCl3)-19.75(s)ppm.
1H NMR(300MHz,CDCl3)0.86(s,9H),1.30(s,3H),1.88–2.02(m,2H),2.16(s,3H),2.99(s,1H),5.18(d,J＝8.8Hz,1H),7.03(d,J＝6.5Hz,2H),7.21–7.26(m,1H),7.30–7.46(m,10H),7.56(d,J＝7.4Hz,2H)ppm.
13C NMR(75MHz,CDCl3)15.74(s,CH3),20.60(s,CH3),22.26(s,3CH3),55.51(s,C),58.32(d,J＝15.3Hz,CH2),63.93(s,CH),71.04(d,J＝5.2Hz,C),126.52(d,J＝0.8Hz,CH),127.58(d,J＝3.7Hz,2CH),127.74(s,CH),128.24(d,J＝3.5Hz,2CH),128.37(s,2CH),128.37(s,CH),128.39(d,J＝2.6Hz,2CH),128.55(s,2CH),128.64(d,J＝5.7Hz,2CH),137.14(d,J＝1.6Hz,C),138.66(d,J＝20.8Hz,C),140.51(s,C),148.49(d,J＝23.2Hz,C),155.35(d,J＝29.7Hz,C),157.89(s,C),162.79(s,C)ppm.
(R)-N-((S)-((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(phenyl)methyl)-2-methylpropane-2-sulfinamide
38％yield；yellow solid
31P NMR(121MHz,CDCl3)-20.98(s)ppm.
1H NMR(300MHz,CDCl3)0.79(s,9H,3CH3),1.25(s,3H,CH3),1.82(t,J＝9.7Hz,1H),2.00(t,J＝9.9Hz,1H),2.08(s,3H,CH3),3.56(s,1H,NH),5.12(d,J＝9.6Hz,1H,CH),7.09(d,J＝4.2Hz,2H),7.23(t,J＝7.3Hz,1H),7.28–7.48(m,12H)ppm.
13C NMR(75MHz,CDCl3)15.20(s,CH3),20.59(s,CH3),22.24(s,3CH3),55.64(s,C),57.57(d,J＝13.3Hz,CH),65.54(s,CH2),70.48(d,J＝5.2Hz,C),126.13(d,J＝1.2Hz,CH),127.21(d,J＝4.7Hz,2CH),127.35(s,CH),127.71(d,J＝4.2Hz,2CH),128.14(s,2CH),128.14(s,CH),128.73(s,2CH),128.90(d,J＝3.1Hz,2CH),129.04(d,J＝3.9Hz,2CH),137.65(d,J＝1.6Hz,C),139.58(d,J＝20.4Hz,C),142.60(s,C),148.29(d,J＝22.6Hz,C),154.63(d,J＝31.3Hz,C),158.29(s,C),164.74(d,J＝1.1Hz,C)ppm.
(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(p-tolyl)methyl)-2-methylpropane-2-sulfinamide
34％yield；yellow solid
31P NMR(121MHz,CDCl3)-19.51(s)ppm.
1H NMR(300MHz,CDCl3)0.85(s,9H),1.28(s,3H),1.94(p,J＝9.8Hz,2H),2.15(s,3H),2.37(s,3H),2.97(s,1H),5.15(d,J＝8.8Hz,1H),7.01(d,J＝6.6Hz,2H),7.17(d,J＝7.8Hz,2H),7.21–7.46(m,11H)ppm.
13C NMR(75MHz,CDCl3)15.72(s,CH3),20.60(s,CH3),21.27(s,CH3),22.26(s,3CH3),55.45(s,C),58.07(d,J＝15.5Hz,CH),63.84(s,CH2),70.99(d,J＝5.2Hz,C),126.47(d,J＝0.9Hz,CH),127.49(d,J＝6.2Hz,2CH),128.21(d,J＝4.9Hz,2CH),128.32(s,2CH),128.32(s,CH),128.35(s,2CH),128.49(d,J＝5.5Hz,2CH),129.29(s,2CH),137.20(d,J＝1.5Hz,C),137.41(s,C),137.41(s,C),138.68(d,J＝20.8Hz,C),148.54(d,J＝20.1Hz,C),155.49(d,J＝29.4Hz,C),157.82(s,C),162.31(d,J＝0.8Hz,C)ppm.
(R)-2-methyl-N-((S)-(5-methyl-3,6-diphenyl-4H-1l2-phosphinin-2-yl)(p-tolyl)methyl)propane-2-sulfinamide
27％yield；yellow solid
31P NMR(121MHz,CDCl3)-20.87(s)ppm.
1H NMR(300MHz,CDCl3)0.76(s,9H,3CH3),1.23(s,3H,CH3),1.81(t,J＝9.7Hz,1H),1.98(t,J＝9.9Hz,1H),2.06(s,3H,CH3),2.34(s,3H,CH3),3.51(s,1H,NH),5.07(d,J＝9.7Hz,1H,CH),7.05–7.14(m,4H),7.18–7.23(m,1H),7.29–7.46(m,9H)ppm.
13C NMR(75MHz,CDCl3)15.17(s,CH3),20.58(s,CH3),21.16(s,CH3),22.23(s,3CH3),55.59(s,C),57.28(d,J＝13.3Hz,CH),65.53(s,CH2),70.43(d,J＝5.1Hz,C),126.10(d,J＝1.1Hz,CH),127.06(d,J＝6.6Hz,2CH),127.19(d,J＝4.3Hz,2CH),127.30(s,CH),128.12(s,2CH),128.89(d,J＝3.7Hz,2CH),129.04(d,J＝3.9Hz,2CH),129.39(s,2CH),137.45(s,C),137.68(d,J＝1.6Hz,C),139.60(d,J＝20.3Hz,C),139.71(s,C),148.31(d,J＝22.7Hz,C),154.74(d,J＝31.0Hz,C),158.27(s,C),164.45(d,J＝1.2Hz,C)ppm.
(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(4-methoxyphenyl)methyl)-2-methylpropane-2-sulfinamide
39％yield；yellow solid
31PNMR(121MHz,CDCl3)-21.03(s)ppm.
1H NMR(300MHz,CDCl3)0.78(s,9H,3CH3),1.25(s,3H,CH3),1.83(t,J＝9.7Hz,1H),2.00(t,J＝9.9Hz,1H),2.07(d,J＝8.9Hz,3H,CH3),3.51(s,1H,NH),3.81(s,3H,OCH3),5.08(d,J＝9.7Hz,1H,CH),6.87(d,J＝8.6Hz,2H),7.08(d,J＝4.9Hz,2H),7.20–7.47(m,11H)ppm.
13C NMR(75MHz,CDCl3)15.20(s,CH3),20.60(s,CH3),22.23(s,3CH3),55.24(s,OCH3),55.57(s,C),56.97(d,J＝13.4Hz,CH),65.54(s,CH2),70.42(d,J＝5.1Hz,C),114.04(s,2CH),126.12(d,J＝1.0Hz,CH),127.31(s,CH),128.14(s,2CH),128.29(d,J＝3.5Hz,2CH),128.41(d,J＝4.2Hz,2CH),128.89(d,J＝5.1Hz,2CH),129.05(d,J＝4.5Hz,2CH),134.85(s,C),137.69(d,J＝1.6Hz,C),139.60(d,J＝20.4Hz,C),148.28(d,J＝22.8Hz,C),154.87(d,J＝31.1Hz,C),158.27(s,C),159.09(s,C),164.21(d,J＝1.1Hz,C)ppm.
(R)-N-((S)-(4-methoxyphenyl)(5-methyl-3,6-diphenyl-4H-1l2-phosphinin-2-yl)methyl)-2-methylpropane-2-sulfinamide
25％yield；yellow solid
31P NMR(121MHz,CDCl3)-21.05(s)ppm.
1H NMR(300MHz,CDCl3)0.77(s,9H,3CH3),1.24(s,3H,CH3),1.83(t,J＝9.7Hz,1H),2.00(t,J＝9.9Hz,1H),2.08(s,3H,CH3),3.50(s,1H,NH),3.81(s,3H,OCH3),5.07(d,J＝9.7Hz,1H,CH),6.87(d,J＝8.7Hz,2H),7.07(d,J＝5.9Hz,2H),7.22(t,J＝7.2Hz,1H),7.32–7.46(m,9H)ppm.
13C NMR(75MHz,CDCl3)15.17(s,CH3),20.58(s,CH3),22.22(s,3CH3),55.25(s,OCH3),55.57(s,C),56.95(d,J＝13.5Hz,CH),65.53(s,CH2),70.41(d,J＝5.1Hz,C),114.02(s,2CH),126.10(d,J＝1.2Hz,CH),127.30(s,CH),128.13(s,2CH),128.29(d,J＝4.7Hz,2CH),128.42(d,J＝4.8Hz,2CH),128.87(d,J＝5.7Hz,2CH),128.99(d,J＝2.8Hz,CH),134.85(s,C),137.68(d,J＝1.7Hz,C),139.58(d,J＝20.4Hz,C),148.25(d,J＝22.8Hz,C),154.85(d,J＝31.1Hz,C),158.29(s,C),159.07(s,C),164.22(d,J＝1.2Hz,C)ppm.
(S)-N-((R)-(4-butylphenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide
30％yield；yellow solid
31P NMR(121MHz,CDCl3)-19.78(s)ppm.
1H NMR(300MHz,CDCl3)0.86(s,9H,3CH3),0.97(t,J＝7.3Hz,3H,CH3),1.30(s,3H,CH3),1.41(dd,J＝14.8,7.4Hz,2H,CH2),1.65(dt,J＝15.3,7.5Hz,2H,CH2),1.90–2.02(m,2H,CH2),2.17(s,3H,3CH3),2.61–2.66(m,2H),2.98(s,1H,NH),5.16(d,J＝8.9Hz,1H,CH),7.04(d,J＝6.5Hz,2H),7.17–7.27(m,3H),7.35–7.48(m,9H)ppm.
13C NMR(75MHz,CDCl3)14.05(s,CH3),15.72(s,CH3),20.62(s,CH3),22.29(s,3CH3),22.57(s,CH2),33.49(s,CH2),35.44(s,CH2),55.45(s,C),58.09(d,J＝15.4Hz,CH),63.92(s,CH2),70.96(d,J＝5.2Hz,C),126.45(d,J＝4.4Hz,CH),127.54(s,CH),128.32(d,J＝3.0Hz,2CH),128.34(s,2CH),128.36(s,2CH),128.38(d,J＝3.3Hz,2CH),128.42(d,J＝2.1Hz,2CH),128.53(s,2CH),137.19(d,J＝1.7Hz,C),137.57(s,C),138.71(d,J＝20.8Hz,C),142.36(s,C),148.54(d,J＝23.3Hz,C),155.52(d,J＝29.5Hz,C),157.82(s,C),162.36(d,J＝0.8Hz,C)ppm.
(R)-N-((S)-(4-butylphenyl)((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide
35％yield；yellow solid
31P NMR(121MHz,CDCl3)-20.86(s)ppm.
1H NMR(300MHz,CDCl3)0.79(s,9H,3CH3),0.95(t,J＝7.3 Hz,3H,CH3),1.25(s,3H,CH3),1.40(dt,J＝14.7,7.2Hz,2H,CH2),1.62(dt,J＝15.3,7.5Hz,2H,CH2),1.92(dt,J＝47.3,9.7Hz,2H,CH2),2.09(s,3H,CH3),2.59–2.64(m,2H,CH2),3.54(s,1H,NH),5.10(d,J＝9.7Hz,1H,CH),7.02–7.17(m,4H),7.23(t,J＝7.2Hz,1H),7.31–7.48(m,9H)ppm.
13C NMR(75MHz,CDCl3)14.00(s,CH3),15.19(s,CH3),20.61(s,CH3),22.25(s,3CH3),22.49(s,CH2),33.56(s,CH2),35.38(s,CH2),55.59(s,C),57.30(d,J＝13.4Hz,CH),65.54(s,CH2),70.42(d,J＝5.2Hz,C),126.10(d,J＝0.9Hz),127.02(d,J＝5.5Hz),127.15(d,J＝4.2Hz),127.31(s),128.13(s),128.71(s),128.90(d,J＝4.1Hz),129.07(d,J＝6.0Hz),137.70(d,J＝1.6Hz),139.62(d,J＝20.3Hz),139.84(s),142.44(s),148.31(d,J＝20.3Hz),154.75(d,J＝31.1Hz),158.25(s),164.39(d,J＝1.0Hz)ppm.
(S)-N-((R)-(4-(tert-butyl)phenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide
39％yield；yellow solid
31P NMR(121MHz,CDCl3)-19.77(s)ppm.
1H NMR(300MHz,CDCl3)0.83(s,9H,3CH3),1.27(s,3H,CH3),1.32(s,9H,3CH3),1.89–2.00(m,2H,CH2),2.13(s,3H,CH3),2.95(s,1H,NH),5.13(d,J＝9.0Hz,1H,CH),7.02(d,J＝4.9Hz,2H),7.21(dd,J＝14.7,7.8Hz,1H),7.29–7.44(m,11H)ppm.
13C NMR(75MHz,CDCl3)15.68(s,CH3),20.62(s,CH3),22.30(s,3CH3),31.41(s,3CH3),34.54(s,C),55.46(s,C),57.99(d,J＝15.6Hz,CH),64.06(s,CH2),70.95(d,J＝5.2Hz,C),125.37(s,2CH),126.41(d,J＝4.0Hz,CH),127.49(s,CH),128.03(d,J＝5.2Hz,2CH),128.30(s,2CH),128.30(s,2CH),128.32(s,2CH),128.45(d,J＝3.0Hz,2CH),137.20(d,J＝4.2Hz,C),137.29(s,C),138.71(d,J＝24.9Hz,C),148.39(d,J＝18.0Hz,C),150.39(s,C),155.48(d,J＝29.4Hz,C),157.82(s,C),162.29(s,C)ppm.
(R)-N-((S)-(4-(tert-butyl)phenyl)((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide
47％yield；yellow solid
31P NMR(121MHz,CDCl3)-20.37(s)ppm.
1H NMR(300MHz,CDCl3)0.78(s,9H,3CH3),1.26(s,3H,CH3),1.34(s,9H,3CH3),1.93(dt,J＝42.1,9.8Hz,2H,CH2),2.09(s,3H,CH3),3.55(s,1H,NH),5.11(d,J＝9.7Hz,1H,CH),7.11(d,J＝6.2Hz,2H),7.22(t,J＝7.1Hz,1H),7.31–7.48(m,11H)ppm.
13C NMR(75MHz,CDCl3)15.19(s,CH3),20.62(s,CH3),22.26(s,3CH3),31.36(s,3CH3),34.55(s,C),55.59(s,C),57.21(d,J＝13.5Hz,CH),65.56(s,CH2),70.43(d,J＝5.1Hz,C),125.60(s,2CH),126.09(d,J＝1.0Hz,CH),126.77(d,J＝6.6Hz,2CH),126.92(d,J＝6.5Hz,2CH),127.30(s,CH),128.12(s,2CH),128.89(d,J＝6.1Hz,2CH),129.07(d,J＝6.4Hz,2CH),137.69(d,J＝1.5Hz,C),139.53(s,C),139.63(d,J＝20.3Hz,C),148.34(d,J＝22.7Hz,C),150.43(d,J＝12.0Hz,C),154.66(d,J＝31.0Hz,C),158.21(s,C),164.39(d,J＝0.6Hz,C)ppm.
(S)-N-((R)-(4-(tert-butoxy)phenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide
37％yield；yellow solid
31P NMR(121MHz,CDCl3)-19.86(s)ppm.
1H NMR(300MHz,CDCl3)0.82(s,9H),1.28(s,3H),1.36(s,9H),2.02–1.86(m,2H),2.14(s,3H),2.92(d,J＝2.2Hz,1H),5.10(dd,J＝9.0,2.2Hz,1H),7.04–6.90(m,4H),7.42–7.18(m,10H)ppm.
13C NMR(75MHz,CDCl3)15.69(s,CH3),20.59(s,CH3),22.25(s,3CH3),28.91(s,3CH3),55.39(s,C),57.74(d,J＝15.2Hz,CH),63.96(s,CH2),70.92(d,J＝5.2Hz,C),78.34(d,J＝2.1Hz,C),123.74(s,2CH),126.48(d,J＝1.1Hz,CH),127.52(s,CH),128.30(d,J＝5.6Hz,2CH),128.34(s,2CH),128.34(s,2CH),128.36(d,J＝2.5Hz,2CH),129.04(d,J＝5.7Hz,2CH),135.06(s,C),137.09(d,J＝1.6Hz,C),138.69(d,J＝20.8Hz,C),148.44(d,J＝21.7Hz,C),154.95(s,C),155.44(d,J＝29.7Hz,C),157.86(s,C),162.52(d,J＝0.8Hz,C)ppm.
(S)-N-((R)-(4-(tert-butoxy)phenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide
39％yield；yellow solid
31P NMR(121MHz,CDCl3)-21.08(s)ppm.
1H NMR(300MHz,CDCl3)0.78(s,9H,3CH3),1.25(s,3H,CH3),1.36(s,9H,3CH3),1.81(t,J＝9.7Hz,1H),1.99(t,J＝9.8Hz,1H),2.07(s,3H,CH3),3.52(d,J＝1.4Hz,1H,NH),5.08(dd,J＝9.7,1.3Hz,1H,CH),6.94(d,J＝8.5Hz,2H),7.08(d,J＝4.8Hz,2H),7.22(t,J＝7.3Hz,1H),7.28–7.32(m,2H),7.34–7.47(m,6H)ppm.
13C NMR(75MHz,CDCl3)15.08(d,J＝16.7Hz,CH3),20.59(s,CH3),22.25(s,3CH3),28.90(s,3CH3),55.57(s,C),57.01(d,J＝13.5Hz,CH),65.55(s,CH2),70.40(d,J＝5.1Hz,C),78.41(d,J＝7.6Hz,C),123.95(s,2CH),126.12(d,J＝4.3Hz,CH),127.29(s,CH),127.58(d,J＝3.7Hz,2CH),127.70(d,J＝4.6Hz,2CH),128.12(s,2CH),128.89(d,J＝4.2Hz,2CH),129.03(d,J＝3.5Hz,2CH),137.21(s,C),137.66(d,J＝1.7Hz,C),139.59(d,J＝20.4Hz,C),148.25(d,J＝22.6Hz,C),154.85(d,J＝31.1Hz,C),154.97(s,C),158.28(s,C),164.24(d,J＝1.1 Hz,C)ppm.
(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(naphthalen-2-yl)methyl)-2-methylpropane-2-sulfinamide
33％yield；yellow solid
31P NMR(121MHz,CDCl3)-18.94(s)ppm.
1H NMR(300MHz,CDCl3)0.87(s,9H),1.28(s,3H),1.93(dt,J＝24.8,9.9Hz,2H),2.15(s,3H),3.10(d,J＝1.6Hz,1H),5.36(d,J＝10.0Hz,1H),7.04(d,J＝6.6Hz,2H),7.18–7.53(m,10H),7.75–7.91(m,5H)ppm.
13C NMR(75MHz,CDCl3)15.76(s,CH3),20.56(s,CH3),22.26(s,3CH3),55.51(s,C),58.64(d,J＝15.7Hz,CH),63.90(s,CH2),71.13(d,J＝5.2Hz,C),126.05(d,J＝2.7Hz,2CH),126.19(d,J＝7.6Hz,CH),126.48(d,J＝4.0Hz,CH),127.65(d,J＝3.8Hz,2CH),127.78(d,J＝3.4Hz,CH),128.16(s,2CH),128.28(s,CH),128.32(s,2CH),128.32(s,CH),128.36(s,CH),128.43(s,CH),133.06(s,C),133.37(s,C),137.27(d,J＝1.6Hz,C),137.89(s,C),138.60(d,J＝20.8Hz,C),148.57(d,J＝23.3Hz,C),155.19(d,J＝29.8Hz,C),157.86(s,C),162.97(d,J＝1.0Hz,C)ppm.
(R)-N-((S)-((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(naphthalen-2-yl)methyl)-2-methylpropane-2-sulfinamide
30％yield；yellow solid
31P NMR(121MHz,CDCl3)-20.55(s)ppm.
1H NMR(300MHz,CDCl3)0.83(s,9H),1.25(s,3H),1.78(dd,J＝18.1,8.4Hz,1H),2.00(t,J＝9.9Hz,1H),2.09(s,3H),3.66(s,1H),5.30(d,J＝10.1Hz,1H),7.13–7.27(m,3H),7.35-7.51(m,10H),7.63(dd,J＝8.5,1.2Hz,1H),7.80–7.85(m,4H)ppm.
13C NMR(75MHz,CDCl3)15.21(s,CH3),20.57(s,CH3),22.27(s,3CH3),55.70(s,C),57.76(d,J＝13.3Hz,CH),65.52(s,CH2),70.54(d,J＝5.2Hz,C),125.44(d,J＝5.9Hz,CH),125.82(d,J＝3.6Hz,CH),126.06(s,CH),126.21(d,J＝5.8Hz,2CH),127.42(s,CH),127.67(s,CH),128.17(s,2CH),128.17(s,2CH),128.51(d,J＝4.3Hz,2CH),128.94(s,CH),129.04(s,CH),133.00(s,C),133.41(s,C),137.71(d,J＝1.6Hz,C),139.62(d,J＝20.4Hz,C),140.06(s,C),148.43(d,J＝22.9Hz,C),154.64(d,J＝31.6Hz,C),158.33(s,C),165.04(d,J＝1.2Hz,C)ppm.
Application example
The application of the compound of the invention is as follows:
the benzophenone derivative is selected as the electron-deficient olefin, so that the silver-catalyzed azomethilidenes-based 1, 3-dipolar cycloaddition reaction is realized. When this asymmetric reaction is catalyzed using a central metal catalyst formed by complexing the relatively conventional chiral ligand BINAP with silver, the reaction proceeds smoothly, but with very low ee values (2% ee). When the chiral P, O ligand of phosphorus chiral center designed and synthesized by the invention is used, AgNTf is found to be used by optimizing conditions such as silver catalyst, different substituent groups on the ligand, solvent, ratio of the catalyst to the ligand, reaction temperature and the like2As a catalyst, II' -e as a ligand best effect. After obtaining the optimal reaction conditions, the substrate applicability of the reaction is further researched through changing the substituent at each position on the reaction substrate, and the corresponding spiro compound can be obtained with high yield, diastereoselectivity and stereoselectivity.
Table one: development testa
a7(0.1mmol),8a(0.2mmol),Ag(I)(0.005mmol),ligand(0.01mmol),Et3N(0.02mmol),DCM(2.0mL),-78℃,24h in a sealed tube.bIsolated Yield.cThe ervalues were determined by chiral HPLC analysis.。
Claims (4)
1.1-phospha norbornadiene compound, which is characterized by having the following general formula:
ar is phenyl, naphthyl, phenyl substituted by C1-5 alkyl or C1-5 alkoxy.
2. The 1-phospha norbornadiene compound according to claim 1, wherein Ar is phenyl, naphthyl, phenyl substituted by methyl, butyl or methoxy or butoxy.
3. The 1-phospha norbornadiene compound according to claim 1, which is selected from the following compounds:
4. a process for the synthesis of 1-heterophosphanorbornadiene compounds according to any of claims 1 to 3, characterized in that it is carried out by:
(1) in N2Under the environment, adding toluene, phosphole A1 and a compound A2 into a Schlenk bottle, reacting in an oil bath at 130-140 ℃, and passing through a column to obtain a compound A3;
(2) in N2Adding dichloromethane, compound A3, hydrochloric acid and silicon dioxide into a Schlenk bottle under the environment, and stirring at room temperature for reaction; after the reaction is completed, H is used2Washing the mixture by using the solvent O,drying and spin-drying to obtain compound A4;
(3) in N2Under the environment, tetrahydrofuran, a compound A4, R-tert-butylimine sulfonate and titanium tetraisopropoxide are added into a Schlenk bottle and subjected to oil bath reaction at the temperature of 40-50 ℃; extracting, drying and separating by column chromatography to obtain a compound A5;
(4) the synthesis method of the compounds II and II' comprises the following steps:
respectively putting the compound A5 in a Schlenk bottle, vacuumizing, filling nitrogen, adding tetrahydrofuran, adding an aryl lithium reagent at the temperature of between 70 ℃ below zero and 78 ℃ below zero, continuing the reaction at the temperature, and adding NH into the reaction system when the reaction is complete4Cl solution, then extracting, combining organic layers, drying, filtering, decompressing, steaming to remove the solvent, and carrying out column chromatography separation to obtain corresponding products II and II';
ar expression is in accordance with claims 1-3, respectively.
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