CN105198935A - Chiral oxazoline palladium coordination compound - Google Patents
Chiral oxazoline palladium coordination compound Download PDFInfo
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- CN105198935A CN105198935A CN201510636902.9A CN201510636902A CN105198935A CN 105198935 A CN105198935 A CN 105198935A CN 201510636902 A CN201510636902 A CN 201510636902A CN 105198935 A CN105198935 A CN 105198935A
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- oxazoline
- reaction
- coordination compound
- chlorobenzene
- chiral
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 title abstract description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004440 column chromatography Methods 0.000 claims abstract description 9
- 229960001701 chloroform Drugs 0.000 claims abstract description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- STVVMTBJNDTZBF-SECBINFHSA-N (2r)-2-amino-3-phenylpropan-1-ol Chemical compound OC[C@H](N)CC1=CC=CC=C1 STVVMTBJNDTZBF-SECBINFHSA-N 0.000 claims abstract description 3
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000010189 synthetic method Methods 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 4
- 238000010992 reflux Methods 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract 2
- 238000006842 Henry reaction Methods 0.000 abstract 1
- 238000006579 Tsuji-Trost allylation reaction Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000004807 desolvation Methods 0.000 abstract 1
- 238000010828 elution Methods 0.000 abstract 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000011592 zinc chloride Substances 0.000 abstract 1
- 235000005074 zinc chloride Nutrition 0.000 abstract 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 13
- -1 phenyl aldehyde Chemical class 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 150000000376 2-oxazolines Chemical class 0.000 description 1
- QMXOFBXZEKTJIK-UHFFFAOYSA-N Glycinol Natural products C1=C(O)C=C2OCC3(O)C4=CC=C(O)C=C4OC3C2=C1 QMXOFBXZEKTJIK-UHFFFAOYSA-N 0.000 description 1
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 1
- 235000005291 Rumex acetosa Nutrition 0.000 description 1
- 240000007001 Rumex acetosella Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000003513 sheep sorrel Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a chiral oxazoline palladium coordination compound. A chemical formula of the chiral oxazoline palladium coordination compound is shown in the specification. A synthetic method of the chiral oxazoline palladium coordination compound includes: adding 5.5782g of o-dicyanobenzene and 19.2782g of D- phenylalaninol into a chlorobenzene solvent to realize a reflux reaction for 60 hours under a water-free oxygen-free condition with ZnCl2 (23.8mol%) serving as a catalyst, and then separating and purifying, namely removing chlorobenzene after reaction, using chloroform for extraction after water addition for dissolution, and adopting column chromatography for purification after desolvation of an extract phase; using petroleum ether and dichloromethane (4:1) for elution, carrying out column chromatography separation to obtain ligand oxazoline after natural volatilization; adding chiral ligand oxazoline and palladium chloride in the chlorobenzene solvent according to a mole ratio of 1:1.0 to realize the reflux reaction for 48 hours, removing chlorobenzene after reaction to obtain red brown solid, adding trichloromethane and ethanol solution for filtering, and allowing filtrate to volatilize naturally to obtain red brown single crystals of the oxazoline palladium coordination compound. The chiral oxazoline palladium coordination compound has a catalytic function in benzaldehyde Henry reaction and allylic alkylation reaction with conversion rates being 85% and 68% respectively.
Description
one, technical field
The present invention relates to a kind of organometallic complex (title complex) and uses thereof, particularly nitrogenous chiral metal organic coordination compound and purposes, is exactly a kind of chiral oxazoline metallic palladium organic coordination compound and uses thereof.
two, background technology
Along with vitochemical development, the application of organometallics in organic synthesis is more and more wide, is one of field of very enlivening in present organic chemistry, has been widely used in organic synthesis.The asymmetric catalysis synthesis of the use chiral ligand that the later stage sixties 20th century occurs and transition metal complex catalysis accelerates the research of chiral drug greatly.The important content of chemical catalysis dissymmetric synthesis is the design of chiral ligand and containing metal catalyzer, thus makes reaction have efficient and high enantioselectivity.Shou Xin oxazoline metallic palladium title complex achieves certain catalytic effect in asymmetric catalysis field in recent years.
Reference:
1.Synthesisofopticallyactivebis(2-oxazolines):crystalstructureofa1,2-bis(2-oxazolinyl)benzene·zincchloridecomplexChemischeBerichte(1991),124,(5),1173-80.
2.Novelchiralbisoxazolineligandswithabiphenylbackbone:preparation,complexation,andapplicationinasymmetriccatalyticreactionsByImai,Yoshitane;Zhang,Wanbin;Kida,Toshiyuki;Nakatsuji,Yohji;Ikeda,Isao,JournalofOrganicChemistry(2000),65(11),3326-3333.
3.Rhodium(III)andRhodium(II)ComplexesofNovelBis(oxazoline)PincerLigandsGerisch,Michael;Krumper,JenniferR.;Bergman,RobertG.;Tilley,T.Don,Organometallics(2003),22(1),47-58。
three, summary of the invention
The present invention aims to provide a kind of Pd-N a metal-organic complex to be applied to catalytic field, and technical problem to be solved is selected neighbour and selected corresponding raw material and set up corresponding method synthesis of chiral catalyzer.
Chirality palladium nitrogen complex alleged by the present invention is by the title complex shown in following chemical formula (I):
Chemical name: [1,2-(4R)-dibenzyl-2-oxazolinyl benzene] palladium chloride complex, is called for short title complex (I).
The synthetic method of this chiral coordination compound (I) comprises reaction, abstraction and purification, it is characterized in that by adjacent dicyanobenzenes 5.5782g and D-phenylalaninol 19.2782g under anhydrous and oxygen-free condition and the anhydrous ZnCl of catalyzer
2(23.8mol%) back flow reaction 60 hours in chlorobenzene solvent, is then separated, purifying, and namely reaction sloughs chlorobenzene after terminating, with chloroform extraction after being dissolved in water, with column chromatography purification after extraction phase precipitation; By sherwood oil and methylene dichloride (4:1) drip washing, column chromatography for separation, volatilize to obtain Pei Ti oxazoline naturally; Again by chirality Pei Ti oxazoline and Palladous chloride according to 1:1.0 mol ratio back flow reaction 48 hours in chlorobenzene solvent, chlorobenzene is sloughed after reaction terminates, obtain red brown solid, after adding trichloromethane and ethanolic soln filtration, filtrate of naturally volatilizing obtains Hong He Se oxazoline palladium complex monocrystalline.
This title complex shows certain catalytic performance in the Henle reaction and allyl group alkylated reaction of phenyl aldehyde, and its transformation efficiency reaches 85% and 68% respectively.
four, accompanying drawing explanation
Fig. 1 is the single crystal diffraction figure of title complex (I).
five, embodiment
(1) preparation of chiral coordination compound (I)
1. the preparation of [1,2-(4R)-dibenzyl-2-oxazolinyl] benzene
ZnCl
21.7109g (12.55mmol), 40ml chlorobenzene, 1,2-dicyanobenzenes 6.5031g (50.7mmol), D-benzene glycinol 21.4037g, at high temperature reflux mixture 24h, stopped reaction, reduce pressure to remove desolventizing,, will remain in 100mL two-mouth bottle, under anhydrous and oxygen-free condition, add anhydride water dissolution, and use CHCl
3(20mLx2) extract, organic phase anhydrous sodium sulfate drying, rotate except desolventizing, by thick product sherwood oil/methylene dichloride (4:1) column chromatography, obtain pale green viscous shape liquid yield 43%; Yellow liquid, [a]
5 d=+25.6o (c=0.349, CH
2cl
2);
1hNMR (500MHz, CDCl
3, 27 DEG C), δ (ppm)=7.71 ~ 7.74 (m, 2H), 7.41 ~ 7.44 (m, 2H), 7.16 ~ 7.30 (m, 10H), 4.57 ~ 4.63 (m, 2H), 4.34 ~ 4.40 (t, J=5.1Hz, 2H), 4.13 ~ 4.18 (t, 2H).
13cNMR41.2367.89,72.03,32.81,126.27,126.39,128.24,128.32,128.45,129.06,129.20,129.20,129.61,129.83,130.19,137.83,163.92.IR:3061,3027,2924,2895,1710,1650,1602,1494,1471,1452,1356,1354,1312,1288,1288,1252,1091,1053,1053,1031,965,918,752,702.HRMS (EI): m/z (%): calcdforC
26h
24n
2o
2: 396.1838; Found:396.1837.
dibenzyl-2-oxazolinyl benzene] preparation of palladium chloride complex
In 100mL two-mouth bottle, under anhydrous and oxygen-free condition, add Palladous chloride 0.4233g (23.7mmol), 1,2-(4R)-dibenzyl-2-oxazolinyl benzene 0.9432g (2.38mmol), mixture at high temperature refluxes 48h by chlorobenzene 30mL, stopped reaction, reduce pressure to remove desolventizing,, by residuum trichloromethane and dissolve with ethanol, naturally volatilize, obtain sorrel title complex and obtain crystal, productive rate 56%; M.p.:230-232 ° of C, [a]
5 d=-19.7o (c=0.0712, CH
3oH) ultimate analysis C
26h
24n
2cl
2o
2pd test value C:54.17%, H, 4.68%, N, 4.93%; Calculated value: C:54.42%, H, 4.22%, N, 4.88%; IR:3443,3067,2973,2920,1637,1628,1591,1504,1455,1439,1389,1320,1249,1209,1073,993,960,949,782,768,759,719,737.Title complex (I) crystal data is as follows:
Empirical formula C26H24Cl2N2O2Pd
Molecular weight 573.77
Temperature 133 (2) K
Wavelength 0.71073
Crystallographic system, Space group Monoclinic system, P2 (1) 2(1) 2(1)
Unit cell parameters a=7.956 (7) α=90 °.
b=12.5079(8)?β=90°
c=21.247(17)?γ=90°.
Volume 2327(3) A^3
Electric density 4,1.637Mg/m^3
Absorption correction parameter 1.054mm^-1
Number of electrons 1160 in unit cell
Crystallographic dimension 0.190x0.140x0.050mm
The scope 1.762to25.498 at Theta angle
Index capture range-the 9<=h<=9 of HKL ,-16<=k<14 ,-22<=l<=25
Collection/independent diffraction data 13413/4278 [R (int)=0.1970]
The data integrity degree 98.7% of theta=30.5
The method Multi Slice Mode of absorption correction
The transmitance 0.7456and0.2912 of minimax
The Matrix least square method of the method F^2 that refine uses
Number/the number of parameters 4278/0/299 of data number/use restriction
The method 1.029 that refine uses
The consistence factor R 1=0.0716 of point diffraction, wR2=0.1528
Identical factor R 1=0.1498, the wR2=0.1866 of observable diffraction
Absolute configuration parameter-0.01(7)
Maximum summit on difference Fourier figure and peak valley 1.610and-1.347e.A^-3
the typical bond distance's data of crystal:
Pd(1)-N(1)2.025(14)
Pd(1)-N(2)2.059(12)
Pd(1)-Cl(1)2.300(5)
Pd(1)-Cl(2)2.304(4)
N(1)-C(7)1.25(2)
N(1)-C(9)1.54(2)
N(2)-C(17)1.28(2)
N(2)-C(19)1.50(2)
O(1)-C(7)1.38(2)
O(1)-C(8)1.47(2)
O(2)-C(17)1.35(2)
O(2)-C(18)1.44(2)
C(1)-C(2)1.41(2)
C(1)-C(17)1.43(3)
C(1)-C(6)1.47(2)
C(2)-C(3)1.38(2)
C(2)-H(2)0.9500
C(3)-C(4)1.37(2)
C(3)-H(3)0.9500
C(4)-C(5)1.41(2)
C(4)-H(4)0.9500
C(5)-C(6)1.34(2)
C(5)-H(5)0.9500
C(6)-C(7)1.49(3)
C(8)-C(9)1.55(2)
C(8)-H(8A)0.9900
C(8)-H(8B)0.9900
C(9)-C(10)1.54(2)
C(9)-H(9)1.0000
C(10)-C(11)1.48(3)
C(10)-H(10A)0.9900
C(10)-H(10B)0.9900
C(11)-C(16)1.40(2)
C(11)-C(12)1.43(2)
C(12)-C(13)1.35(3)
C(12)-H(12)0.9500
C(13)-C(14)1.42(3)
C(13)-H(13)0.9500
C(14)-C(15)1.41(3)
C(14)-H(14)0.9500
C(15)-C(16)1.34(3)
C(15)-H(15)0.9500
C(16)-H(16)0.9500
C(18)-C(19)1.56(2)
C(18)-H(18A)0.9900
C(18)-H(18B)0.9900
C(19)-C(20)1.53(2)
C(19)-H(19)1.0000
C(20)-C(21)1.48(2)
C(20)-H(20A)0.9900
C(20)-H(20B)0.9900
C(21)-C(22)1.38(2)
C(21)-C(26)1.43(2)
C(22)-C(23)1.37(3)
C(22)-H(22)0.9500
C(23)-C(24)1.36(3)
C(23)-H(23)0.9500
C(24)-C(25)1.37(3)
C(24)-H(24)0.9500
C(25)-C(26)1.37(2)
C(25)-H(25)0.9500
C(26)-H(26)0.9500
the typical bond angle data of crystal:
N(1)-Pd(1)-N(2)88.2(5)
N(1)-Pd(1)-Cl(1)177.1(4)
N(2)-Pd(1)-Cl(1)89.4(4)
N(1)-Pd(1)-Cl(2)93.4(4)
N(2)-Pd(1)-Cl(2)175.9(4)
Cl(1)-Pd(1)-Cl(2)89.09(18)
C(7)-N(1)-C(9)108.7(14)
C(7)-N(1)-Pd(1)126.1(11)
C(9)-N(1)-Pd(1)125.1(11)
C(17)-N(2)-C(19)110.4(13)
C(17)-N(2)-Pd(1)124.5(13)
C(19)-N(2)-Pd(1)123.4(11)
C(7)-O(1)-C(8)104.5(14)
C(17)-O(2)-C(18)107.6(13)
C(2)-C(1)-C(17)120.3(16)
C(2)-C(1)-C(6)115.0(17)
C(17)-C(1)-C(6)124.5(16)
C(3)-C(2)-C(1)122.4(16)
C(3)-C(2)-H(2)118.8
C(1)-C(2)-H(2)118.8
C(4)-C(3)-C(2)120.9(17)
C(4)-C(3)-H(3)119.6
C(2)-C(3)-H(3)119.6
C(3)-C(4)-C(5)119.0(18)
C(3)-C(4)-H(4)120.5
C(5)-C(4)-H(4)120.5
C(6)-C(5)-C(4)121.0(17)
C(6)-C(5)-H(5)119.5
C(4)-C(5)-H(5)119.5
C(5)-C(6)-C(1)121.6(16)
C(5)-C(6)-C(7)117.0(16)
C(1)-C(6)-C(7)121.3(17)
N(1)-C(7)-O(1)117.3(16)
N(1)-C(7)-C(6)131.8(16)
O(1)-C(7)-C(6)110.9(16)
O(1)-C(8)-C(9)105.3(13)
O(1)-C(8)-H(8A)110.7
C(9)-C(8)-H(8A)110.7
O(1)-C(8)-H(8B)110.7
C(9)-C(8)-H(8B)110.7
H(8A)-C(8)-H(8B)108.8
C(10)-C(9)-N(1)111.8(13)
C(10)-C(9)-C(8)111.5(15)
N(1)-C(9)-C(8)98.7(13)
C(10)-C(9)-H(9)111.4
N(1)-C(9)-H(9)111.4
C(8)-C(9)-H(9)111.4
C(11)-C(10)-C(9)116.9(15)
C(11)-C(10)-H(10A)108.1
C(9)-C(10)-H(10A)108.1
C(11)-C(10)-H(10B)108.1
C(9)-C(10)-H(10B)108.1
H(10A)-C(10)-H(10B)107.3
C(16)-C(11)-C(12)116.5(18)
C(16)-C(11)-C(10)122.1(17)
C(12)-C(11)-C(10)121.5(16)
C(13)-C(12)-C(11)119.8(18)
C(13)-C(12)-H(12)120.1
C(11)-C(12)-H(12)120.1
C(12)-C(13)-C(14)122.8(18)
C(12)-C(13)-H(13)118.6
C(14)-C(13)-H(13)118.6
C(15)-C(14)-C(13)116.8(19)
C(15)-C(14)-H(14)121.6
C(13)-C(14)-H(14)121.6
C(16)-C(15)-C(14)120(2)
C(16)-C(15)-H(15)119.9
C(14)-C(15)-H(15)119.9
C(15)-C(16)-C(11)123.9(19)
C(15)-C(16)-H(16)118.0
C(11)-C(16)-H(16)118.0
N(2)-C(17)-O(2)115.4(16)
N(2)-C(17)-C(1)131.5(17)
O(2)-C(17)-C(1)113.0(15)
O(2)-C(18)-C(19)105.5(14)
O(2)-C(18)-H(18A)110.6
C(19)-C(18)-H(18A)110.6
O(2)-C(18)-H(18B)110.6
C(19)-C(18)-H(18B)110.6
H(18A)-C(18)-H(18B)108.8
N(2)-C(19)-C(20)110.4(14)
N(2)-C(19)-C(18)100.2(14)
C(20)-C(19)-C(18)111.9(14)
N(2)-C(19)-H(19)111.3
C(20)-C(19)-H(19)111.3
C(18)-C(19)-H(19)111.3
C(21)-C(20)-C(19)116.5(13)
C(21)-C(20)-H(20A)108.2
C(19)-C(20)-H(20A)108.2
C(21)-C(20)-H(20B)108.2
C(19)-C(20)-H(20B)108.2
H(20A)-C(20)-H(20B)107.3
C(22)-C(21)-C(26)117.4(16)
C(22)-C(21)-C(20)121.9(17)
C(26)-C(21)-C(20)120.7(16)
C(23)-C(22)-C(21)122.9(18)
C(23)-C(22)-H(22)118.6
C(21)-C(22)-H(22)118.6
C(24)-C(23)-C(22)118.6(18)
C(24)-C(23)-H(23)120.7
C(22)-C(23)-H(23)120.7
C(23)-C(24)-C(25)120.8(18)
C(23)-C(24)-H(24)119.6
C(25)-C(24)-H(24)119.6
C(26)-C(25)-C(24)121.5(18)
C(26)-C(25)-H(25)119.2
C(24)-C(25)-H(25)119.2
C(25)-C(26)-C(21)118.9(17)
C(25)-C(26)-H(26)120.6
C(21)-C(26)-H(26)120.6
(2), Henle reaction application
Get 0.10mmol title complex (I) (catalytic amount is 10%) in the little flask of 25mL, add the tetrahydrofuran solution of 2 milliliters, then, in above-mentioned solution, add the phenyl aldehyde of 0.1mL and the Nitromethane 99Min. of 0.5mL, stirring at normal temperature, react 48 hours, with sherwood oil/eluent methylene chloride, carry out column chromatography, productive rate 85%.
1hNMR (300MHz, CDCl
3).
(3) allyl group alkylated reaction application
The title complex I(catalytic amount of getting 0.20mmol is 20%) in the little flask of 25mL, add the dichloromethane solution of 2 milliliters, then, the phenyl aldehyde of 0.1mL and the allyl trimethyl silane of 0.3mL is added in above-mentioned solution, stirring at normal temperature, react after 48 hours, carry out nmr analysis, transformation efficiency: 68%;
1hNMR (300MHz, CDCl
3) 7.27 ~ 7.33 (m, 5H, Ar-H), 5.79 ~ 5.80 (m, 1H), 5.12 ~ 5.17 (m, 2H ,-CH
2), 4.71(d, J=5Hz, 1H), 2.49 ~ 2.50 (m, 2H), 2.28(s, 1H).
Under applicant's parallel condition, done the another two compounds II of similar this complex structure (I) and III catalysis Henle reaction and allyl group alkylated reaction, its catalytic effect is shown in following Application Example; Its structural formula is as follows:
IIIII
Henle reaction is applied
Get 0.10mmol title complex II and III(catalytic amount is 10%) in the little flask of 25mL, add the tetrahydrofuran solution of 2 milliliters, then, in above-mentioned solution, add the phenyl aldehyde of 0.1mL and the Nitromethane 99Min. of 0.5mL, stirring at normal temperature, react 48 hours, with sherwood oil/eluent methylene chloride, carry out column chromatography, productive rate is respectively 46%., and 58%
1hNMR (300MHz, CDCl
3), 8.00 (d, J=23Hz, 1H), 7.47 ~ 7.63 (m, 6H).
Allyl group alkylated reaction is applied
Title complex II and the III(catalytic amount of getting 0.20mmol are 20%) in the little flask of 25mL, add the dichloromethane solution of 2 milliliters, then, the phenyl aldehyde of 0.1mL and the allyl trimethyl silane of 0.3mL is added in above-mentioned solution, stirring at normal temperature, reacts after 48 hours, carries out nmr analysis, transformation efficiency is respectively: 28%, and 36%;
1hNMR (300MHz, CDCl
3) 7.27 ~ 7.33 (m, 5H, Ar-H), 5.79 ~ 5.80 (m, 1H), 5.12 ~ 5.17 (m, 2H ,-CH
2), 4.71(d, J=5Hz, 1H), 2.49 ~ 2.50 (m, 2H), 2.28(s, 1H).
Claims (2)
1. a chiral oxazoline palladium complex, its chemical formula is as follows:
（Ⅰ）
。
2. the synthetic method of title complex according to claim 1 (I), comprises reaction, abstraction and purification, it is characterized in that by adjacent dicyanobenzenes 5.5782g and D-phenylalaninol 19.2782g under anhydrous and oxygen-free condition and the anhydrous ZnCl of catalyzer
2(23.8mol%) back flow reaction 60 hours in chlorobenzene solvent, is then separated, purifying, and namely reaction sloughs chlorobenzene after terminating, with chloroform extraction after being dissolved in water, with column chromatography purification after extraction phase precipitation; Be 4:1 drip washing by volume with sherwood oil and methylene dichloride, column chromatography for separation, volatilize to obtain Pei Ti oxazoline naturally; Again by chirality Pei Ti oxazoline and Palladous chloride according to 1:1.0 mol ratio back flow reaction 48 hours in chlorobenzene solvent, chlorobenzene is sloughed after reaction terminates, obtain red brown solid, after adding trichloromethane and ethanolic soln filtration, filtrate of naturally volatilizing obtains Hong He Se oxazoline palladium complex monocrystalline.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163085A (en) * | 2017-06-09 | 2017-09-15 | 合肥祥晨化工有限公司 | A kind of preparation of chiral platinum complex crystal and purposes |
| CN107337652A (en) * | 2017-07-05 | 2017-11-10 | 合肥祥晨化工有限公司 | A kind of Chiral oxazoline cobalt complex and purposes |
| CN108727290A (en) * | 2018-04-12 | 2018-11-02 | 合肥工业大学 | A kind of chiral oxazoline palladium complex and purposes |
| CN110305167A (en) * | 2019-06-18 | 2019-10-08 | 合肥工业大学 | Preparation and application of a chiral platinum complex |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163085A (en) * | 2017-06-09 | 2017-09-15 | 合肥祥晨化工有限公司 | A kind of preparation of chiral platinum complex crystal and purposes |
| CN107337652A (en) * | 2017-07-05 | 2017-11-10 | 合肥祥晨化工有限公司 | A kind of Chiral oxazoline cobalt complex and purposes |
| CN108727290A (en) * | 2018-04-12 | 2018-11-02 | 合肥工业大学 | A kind of chiral oxazoline palladium complex and purposes |
| CN110305167A (en) * | 2019-06-18 | 2019-10-08 | 合肥工业大学 | Preparation and application of a chiral platinum complex |
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