CN104628788A

CN104628788A - Chiral oxazoline palladium complex and use thereof

Info

Publication number: CN104628788A
Application number: CN201510068969.7A
Authority: CN
Inventors: 罗梅
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-02-11
Filing date: 2015-02-11
Publication date: 2015-05-20

Abstract

The invention discloses a chiral oxazoline palladium complex which has a chemical formula as shown in the description. The synthesis method of the chiral complex (I) comprises the following steps of putting 50.75mmol of o-dicyanobenzene and 21.4037g of D-phenylglycinol and a catalyst of 24.7 mol% anhydrous ZnCl2 into a chlorobenzene solution for reflux reaction for 60 hours under an anhydrous and anaerobic condition, then separating, purifying, leaching with petroleum ether and dichloromethane with the volume ratio of 4:1, carrying out column chromatography isolation, and naturally volatilizing to obtain oxazoline; putting the chiral ligand oxazoline and palladium chloride according to a molar ratio of 1:1.49 into a chlorobenzene solution for reflux reaction for 48 hours, removing chlorobenzene after reaction so as to obtain bronzing solid, adding trichloromethane and ethanol solution and filtering, naturally volatilizing the filter liquor to obtain bronzing oxazoline palladium complex single crystals. The chiral complex (I) shows certain catalytic performance during Henry reaction, Nitrile silicification reaction and Baylis-Hillman reaction of benzaldehyde, and the conversion ratio respectively reaches 86%, 62% and 28%.

Description

A kind of chiral oxazoline palladium complex and purposes

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. Highly enantioselective Pd(II)-catalyzed Wacker-type cyclization of 2-allylphenols by use of bisoxazoline ligands with axis-unfixed biphenyl backbone Wang, Feijun et al, Tetrahedron Letters, 48(24), 4179-4182; 2007

2 Incorporation of a Phebox Rhodium Complex into apo-?Myoglobin Affords a Stable Organometallic Protein Showing Unprecedented Arrangement of the Complex in the Cavity Satake, Yuh; Abe, Satoshi; Okazaki, Seiji; Ban, Noritaka; Hikage, Tatsuo; Ueno, Takafumi; Nakajima, Hiroshi; Suzuki, Atsuo; Yamane, Takashi; Nishiyama, Hisao; et al , Organometallics (2007), 26(20), 4904-4908.

3. Novel chiral bisoxazoline ligands with a biphenyl backbone: preparation, complexation, and application in asymmetric catalytic reactions By Imai, Yoshitane; Zhang, Wanbin; Kida, Toshiyuki; Nakatsuji, Yohji; Ikeda, Isao ,Journal of Organic Chemistry (2000), 65(11), 3326-3333.

4. Rhodium(III) and Rhodium(II) Complexes of Novel Bis(oxazoline) Pincer Ligands Gerisch, Michael; Krumper, Jennifer R.; Bergman, Robert G.; 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)-phenylbenzene-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 50.75mmol and D-benzene glycinol 21.4037g under anhydrous and oxygen-free condition and the anhydrous ZnCl of catalyzer ₂(24.7 mol%) 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 1:1.49 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 of phenyl aldehyde, nitrile silicification reaction and Baylis-Hillman reaction, and its transformation efficiency reaches 86%, 62% and 28% 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

1. the preparation of [1,2-(4R)-phenylbenzene-2-oxazolinyl] benzene

In 100mL two-mouth bottle, under anhydrous and oxygen-free condition, add anhydrous ZnCl ₂1.7109g (12.55mmol),

40ml chlorobenzene, 1,2-dicyanobenzenes 6.5031g (50.75mmol), D-benzene glycinol 21.4037g, at high temperature reflux mixture 24h, stopped reaction, reduces pressure to remove desolventizing, by residuum 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 [a] ⁵ _d=-64.8o (c=0.52, CHCl ₃); ¹hNMR (500MHz, CDCl ₃, 27 DEG C), δ (ppm)=7.86 ~ 7.89 (m, 2H), 7.52 ~ 7.55 (m, 2H), 7.23 ~ 7.36 (m, 10H), 4.49 ~ 4.59 (m, 2H), 4.21 ~ 4.27 (t, J=0.61Hz, 2H), 3.99 ~ 4.03 (t, J=0.84Hz, 2H), 3.14 ~ 3.20 (dd, J=5.57,5.48Hz, 2H), 2.73 ~ 2.75 (dd, J=4.24,4.27Hz, 2H). ¹³cNMR, 41.23,67.89,72.03,126.27,128.24,128.32,129.06,129.20,129.61,130.19,137.83,163.92.IR:3061,3029,2956,2924,2897,2854,1651,1601,1494,1470,1454,1356,1313,1303,1236,1090,1054,1032,971,950,901,893,758,700.HRMS (EI): m/z (%): calcd for C ₂₄h ₂₀n ₂o ₂: 368.1525; Found:368.1479.

2. the preparation of [1,2-(4R)-phenylbenzene-2-oxazolinyl benzene] palladium chloride complex

In 100mL two-mouth bottle, under anhydrous and oxygen-free condition, add Palladous chloride 0.8733g (4.92mmol), 1,2-(4R)-phenylbenzene-2-oxazolinyl benzene 1 .2145g (3..30mmol), mixture at high temperature refluxes 48h by chlorobenzene 30mL, stopped reaction, reduces 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.:208-210 ° of C, [a] ⁵ _d=-1263.7o (c=0.0364, CHCl ₃): ¹hNMR (600MHz, CDCl ₃, 27 DEG C), δ (ppm)=8.01-8.13 (m, 5H), (7.62-7.69 s, 1H), 7.10-7.35 (m, 6H), 5.57 (t, J=0.6Hz, 1H), 5.22 (t, J=0.6Hz, 1H), 4.97 (t, J=0.3Hz, 1H), 3.58-4.76 (m, 2H), 4.34-4.38 (m, 1H) ¹³cNMR:69.2,71.5,76.4,76.9,125.7,126.4,128.5,129.1; 129.3,129.5,129.7,129.9,120.0,130.1,130.3,130.9; 131.0,133.9,134.0,136.9,140.0,147.0,164.9,166.7; Ultimate analysis C ₂₄h ₂₀n ₂cl ₂o ₂zn C:52.19%, H, 3.48%, N, 5.31%; Calculated value: C:52.82%, H, 3.69 %, N, 5.13 %; IR:3030,2161,1979,1711,1629,1592,1494,1454,1377,1315,1278,1233,1207,1128,1070,1042,1029,930,917,761,719,699,651,592.

Title complex (I) crystal data is as follows:

Empirical formula C24 H20Cl2 N2 O2 Pd

Molecular weight 545.72

Temperature 296 (2) K

Wavelength 1.54178

Crystallographic system, Space group Monoclinic system, P2 (1)

Unit cell parameters a=9.9982 (8) α=90 °.

b = 12.5079(8)? β = 92.822(6)°

c = 10.5023(8) ? γ = 90 °.

Volume 1311.79(16) A^3

Electric density 2,1.382Mg/m^3

Absorption correction parameter 7.746 mm^-1

Number of electrons 548 in unit cell

Crystallographic dimension 0.121x 0.088x 0.043 mm

Scope 4.215 to 64.937 at Theta angle

Index capture range-the 11<=h<=11 of HKL ,-14<=k<14 ,-12<=l<=12

Collection/independent diffraction data 4227/ 4365 [R (int)=0.2134]

The data integrity degree 92.1% of theta=30.5

The method Multi Slice Mode of absorption correction

Transmitance 0.7530 and 0.3721 of minimax

The Matrix least square method of the method F^2 that refine uses

Number/the number of parameters 4227/91/281 of data number/use restriction

The method 0.972 that refine uses

The consistence factor R 1=0.0988, wR2=0.2373 of point diffraction

The identical factor R 1=0.1521, wR2=0.2777 of observable diffraction

Absolute configuration parameter 0.0015(9)

Maximum summit on difference Fourier figure and peak valley 1.826 and-2.339e.A^-3

the typical bond distance's data of crystal:

Pd(1)-N(1) 1.98(2)

Pd(1)-N(2) 2.080(19)

Pd(1)-Cl(2) 2.266(7)

Pd(1)-Cl(1) 2.277(7)

N(1)-C(1) 1.24(3)

N(1)-C(3) 1.60(3)

N(2)-C(16) 1.31(3)

N(2)-C(18) 1.47(4)

O(1)-C(1) 1.38(3)

O(1)-C(2) 1.46(3)

O(2)-C(16) 1.29(3)

O(2)-C(17) 1.42(4)

the typical bond angle data of crystal:

N(1)-Pd(1)-N(2) 85.9(9)

N(1)-Pd(1)-Cl(2) 175.9(6)

N(2)-Pd(1)-Cl(2) 93.8(7)

N(1)-Pd(1)-Cl(1) 90.2(7)

N(2)-Pd(1)-Cl(1) 175.8(7)

Cl(2)-Pd(1)-Cl(1) 90.1(3)

C(1)-N(1)-C(3) 105(2)

C(1)-N(1)-Pd(1) 127.5(16)

C(3)-N(1)-Pd(1) 126.1(14)

C(16)-N(2)-C(18) 109(2)

C(16)-N(2)-Pd(1) 123.3(18)

C(18)-N(2)-Pd(1) 125.7(18)

C(1)-O(1)-C(2) 104.1(17)

C(16)-O(2)-C(17) 106(2)

N(1)-C(1)-O(1) 121(2)

N(1)-C(1)-C(10) 127(2)

O(1)-C(1)-C(10) 112.5(16)

O(1)-C(2)-C(3) 108(2)

O(1)-C(2)-H(2A) 110.0

C(3)-C(2)-H(2A) 110.0

O(1)-C(2)-H(2B) 110.0

C(3)-C(2)-H(2B) 110.0

H(2A)-C(2)-H(2B) 108.4

C(2)-C(3)-C(4) 120(2)

C(2)-C(3)-N(1) 101.3(17)

C(4)-C(3)-N(1) 107(2)

C(2)-C(3)-H(3) 109.3

C(4)-C(3)-H(3) 109.3

N(1)-C(3)-H(3) 109.3

C(5)-C(4)-C(9) 121(3)

C(5)-C(4)-C(3) 123(3)

C(9)-C(4)-C(3) 116(3)

C(4)-C(5)-C(6) 121(3)

C(4)-C(5)-H(5) 119.3

C(6)-C(5)-H(5) 119.3

C(5)-C(6)-C(7) 117(3)

C(5)-C(6)-H(6) 121.6

C(7)-C(6)-H(6) 121.6

C(8)-C(7)-C(6) 124(3)

C(8)-C(7)-H(7) 118.1

C(6)-C(7)-H(7) 118.1

C(7)-C(8)-C(9) 116(3)

C(7)-C(8)-H(8) 121.8

C(9)-C(8)-H(8) 121.8

C(4)-C(9)-C(8) 120(3)

C(4)-C(9)-H(9) 120.0

C(8)-C(9)-H(9) 120.0

C(15)-C(10)-C(11) 120(2)

C(15)-C(10)-C(1) 122(2)

C(11)-C(10)-C(1) 118(2)

C(12)-C(11)-C(10) 120(3)

C(12)-C(11)-H(11) 119.8

C(10)-C(11)-H(11) 119.8

C(13)-C(12)-C(11) 119(3)

C(13)-C(12)-H(12) 120.4

C(11)-C(12)-H(12) 120.4

C(12)-C(13)-C(14) 126(3)

C(12)-C(13)-H(13) 116.9

C(14)-C(13)-H(13) 116.9

C(15)-C(14)-C(13) 111(3)

C(15)-C(14)-H(14) 124.3

C(13)-C(14)-H(14) 124.3

C(10)-C(15)-C(14) 122(2)

C(10)-C(15)-C(16) 126(2)

C(14)-C(15)-C(16) 111(3)

O(2)-C(16)-N(2) 115(2)

O(2)-C(16)-C(15) 120(2)

N(2)-C(16)-C(15) 125(2)

O(2)-C(17)-C(18) 110(3)

O(2)-C(17)-H(17A) 109.6

C(18)-C(17)-H(17A) 109.6

O(2)-C(17)-H(17B) 109.6

C(18)-C(17)-H(17B) 109.6

H(17A)-C(17)-H(17B) 108.1

C(17)-C(18)-N(2) 100(2)

C(17)-C(18)-C(19) 117(3)

N(2)-C(18)-C(19) 111(3)

C(17)-C(18)-H(18) 109.8

N(2)-C(18)-H(18) 109.8

C(19)-C(18)-H(18) 109.8

C(20)-C(19)-C(24) 117(3)

C(20)-C(19)-C(18) 123(3)

C(24)-C(19)-C(18) 121(3)

C(19)-C(20)-C(21) 120(3)

C(19)-C(20)-H(20) 119.9

C(21)-C(20)-H(20) 119.9

C(22)-C(21)-C(20) 125(4)

C(22)-C(21)-H(21) 117.7

C(20)-C(21)-H(21) 117.7

C(21)-C(22)-C(23) 116(4)

C(21)-C(22)-H(22) 121.8

C(23)-C(22)-H(22) 121.8

C(22)-C(23)-C(24) 127(3)

C(22)-C(23)-H(23) 116.6

C(24)-C(23)-H(23) 116.6

C(23)-C(24)-C(19) 115(3)

C(23)-C(24)-H(24) 122.4

C(19)-C(24)-H(24) 122.4

(2), Henle reaction application

the preparation of 1.E-beta-nitrostyrene

Get 0.15mmol title complex (I) (catalytic amount is 15%) in the little flask of 25mL, add the tetrahydrofuran solution of 2 milliliters, then, the phenyl aldehyde of 0.1mL and the Nitromethane 99Min. of 0.5mL is added in above-mentioned solution, stirring at normal temperature, reacts 72 hours, with sherwood oil/eluent methylene chloride, carry out column chromatography, productive rate 86 %. ¹hNMR (300MHz, CDCl ₃), 8.00 (d, J=23Hz, 1H), 7.47 ~ 7.63 (m, 6H).

(3), nitrile silicification reaction application

2-phenyl-2-(three silyloxy) preparation of acetonitrile

0.15mmol Compound I, phenyl aldehyde 0.1mL, TMSCN 0.3 ml (3.3mmol) in succession add under 20 ~ 30 C, after 72h, add shrend and go out after post layer that (sherwood oil/methylene dichloride: 5/1), obtains colourless oil liquid, transformation efficiency: 68% ¹hNMR (300MHz, CDCl3) 7.56 – 7.59 (m, 0.9 Hz, 2H), 7.31 – 7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H). ¹³c NMR (75 MHz, CDCl ₃) 136.1,128.8 (x2), 126.2 (x2), 119.1,63.5 ,-0.39 (x3).

(4) Baylis-Hillman reactive applications

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; phenyl aldehyde and the 0.5mL methyl acrylate of 0.1mL is added in above-mentioned solution; stirring at normal temperature; after reacting little 72 hours, carry out nmr analysis, transformation efficiency: 28 %; ¹hNMR (300MHz, CDCl ₃) 7.20 ~ 7.41 (m, 5H, Ar-H), 6.30 (s, 1H), 5.45 (s, 1H), 3.70 (s, 3H), 3.15 (s, 1H).

Claims

1. a chiral oxazoline palladium complex, its chemical formula is as follows:

（Ⅰ）。

2. chiral oxazoline title complex (I) according to claim 1, at 296(2) at k temperature, on the X-ray single crystal diffraction instrument of Oxford, diffraction data is collected with ω-θ scan mode with the MoK alpha-ray (λ=0.71073) through graphite monochromator monochromatization, it is characterized in that crystal belongs to oblique system, spacer P2 (1), unit cell parameters: a=9.9982 (8), α=90 °; B=12.5079 (8), β=92.822(6) °; C=10.5023 (8), γ=90 °.

3. the synthetic method of title complex according to claim 1 (I), comprise reaction, abstraction and purification, its feature by adjacent dicyanobenzenes 50.75mmol and D-benzene glycinol 21.4037g under anhydrous and oxygen-free condition and the anhydrous ZnCl2(2.7 mol% of catalyzer back flow reaction 60 hours in chlorobenzene solvent, then separation, purifying, 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 1:1.49 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.

4. this chiral oxazoline title complex (I) shows certain catalytic performance in the Henle reaction of phenyl aldehyde, nitrile silicification reaction and Baylis-Hillman reaction, and its transformation efficiency reaches 86%, 62% and 28% respectively.