CN105198935A

CN105198935A - Chiral oxazoline palladium coordination compound

Info

Publication number: CN105198935A
Application number: CN201510636902.9A
Authority: CN
Inventors: 罗梅
Original assignee: Hefei Xiangchen Chemical Engineering Co Ltd
Current assignee: Hefei Xiangchen Chemical Engineering Co Ltd
Priority date: 2015-10-02
Filing date: 2015-10-02
Publication date: 2015-12-30

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

A kind of chiral oxazoline palladium complex

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

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.