CN114369248B - Chiral silicon-containing polyester and synthesis method thereof - Google Patents
Chiral silicon-containing polyester and synthesis method thereof Download PDFInfo
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Abstract
The invention discloses a chiral silicon-containing polyester and synthesis thereofThe method takes a complex of a bisoxazoline ligand of cheap metal copper as a catalyst to prepare the chiral silicon-containing polyester by catalyzing enantioselective insertion polymerization of a diazo compound (monomer I) and silane (monomer II). The invention has high reaction stereoselectivity, the enantioselectivity can reach 99.2 percent, and the diastereoselectivity can reach 9.1: 1. The chiral polyester has a novel main chain structure and a maximum number average molecular weight of 1.42 multiplied by 10 4 . The reaction operation is simple, convenient and practical, the condition is mild, and the substrate range is wide.
Description
Technical Field
The invention belongs to the technical field of silicon-containing polymer synthesis, and particularly relates to chiral silicon-containing polyester and a method for synthesizing the chiral silicon-containing polyester with a novel structure by using copper bisoxazoline ligand complex catalysis.
Background
Inspired by natural chiral polymers in nature, research on artificially synthesized chiral polymers gradually attracts people's attention. At present, synthetic chiral polymers have been applied to chiral catalysis, separation media, biomaterials, and nonlinear optical materials (reference: Itsuno, S.polymeric chiral catalyst design and chiral polymer synthesis [ M ]. New Jersey: John Wiley & Sons, Inc.2011.).
The polymerization of chiral monomers is a simple and straightforward method for synthesizing optically active polymers (ref.di: Ciardeli, F.; Altomare, A.; Carlini, C.prog.Polym.Sci.1991,16, 259-. However, this process also suffers from disadvantages such as high cost and commercial unavailability of chiral monomers. In contrast, chiral polymers are more practical and economical to synthesize using asymmetric polymerization of achiral monomers (reference three (a) Nagata, y.; Takeda, r.; Suginome, m.acs cent.sci.2019,5,1235-1240.(b) Chu, j. -h.; Xu, x. -h.; Kang, s. -m.; Liu, n.; Wu, z. -q.j.am.chem.soc.2018,140,17773-17781.(c) Nozaki, k.; Sato, n.; Takaya, h.j.am.chem.soc.1995,117, 9911-9912.). To date, asymmetric polymerization has been successfully applied to the synthesis of various types of chiral polymers. However, the optical purity of most chiral polymers is still characterized by optical rotation and circular dichroism, and the two methods cannot realize accurate characterization of the optical purity. Therefore, accurate characterization of the optical purity of chiral polymers remains a challenging research topic (reference four (a) Lu, x. -b.; Darensbourg, d.j. chem. soc. rev.2012,41, 1462-containing 1484.(b) Childers, m.i., Longo, j.m., Zee, n.j.v.; lapoine, a.m., coats, g.w. chem. rev.2014,114, 8129-8152.).
As an efficient method for constructing carbon-carbon bonds and carbon-hetero bonds, carbene insertion reactions have been widely used in organic synthesis (reference five: Ford, A.; Miel, H.; Ring, A.; Slattery, C.N.; Maguire, A.R.; McKervey, M.A.chem.Rev.2015,115, 9981-10080.). This method is also gradually used for the synthesis of polymers having a novel main chain structure. In 2010, Rh was used by Ihara group 2 (OAc) 4 As a catalyst, a three-component polycondensation reaction of a diazocarbonyl compound, phenol and tetrahydrofuran was effected to give a novel polyether ketone (reference six: Ihara, E.; Saiki, K.; Goto, Y.; Itoh, T.; Inoue, K. macromolecules 2010,43, 4589-. Thereafter, dicarboxylic acids were also applied to the three-component polycondensation reaction (ref.hepta: Ihara, E.; Hara, Y.; Itoh, T.; Inoue, K.macromolecules 2011,44, 5955-. Furthermore, the Yan group reported that rhodium catalyzed oxygen-hydrogen bond insertion polymerization of diazo compounds with carboxylic acids synthesized a series of polyesters (ref. eight: Wang, X.; Ding, Y.; Tao, Y.; Wang, Z.; Yan, J.Polym. chem.2020,11, 1708-. Recently, Ihara group has also successfully achieved nitrogen-hydrogen bond insertion polymerization of diazo compounds with aromatic amines using ruthenium catalysts (ref. nine: Shimomoto, H.; Mukai, H.; Bekku, H.; Itoh, T.; Ihara, E. macromolecules 2017,50, 9233-. Although the silicon-hydrogen bond insertion reaction of carbenes has been well developed, this method has not been applied to the synthesis of polymers.
Disclosure of Invention
The invention aims to provide chiral silicon-containing polyester and a synthesis method thereof, and the method is used for catalyzing enantioselective insertion polymerization of a silane monomer and a diazo compound by taking a complex of cheap metal copper and a bisoxazoline ligand as a catalyst to prepare the chiral silicon-containing polyester. The invention applies asymmetric silicon-hydrogen bond insertion reaction to the synthesis of optically active polymers. Meanwhile, in order to accurately characterize the optical purity of the chiral polymer, an ester group is introduced into the structure of the diazo compound to facilitate the degradation of the polymerization product and the characterization of the stereoselectivity of the polymerization reaction.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a chiral silicon-containing polyester having the structure shown in formula iii:
in the formula: r 1 And R 2 All of which are aryl groups, and preferably aryl groups having various substituents, such as phenyl, 4-fluorophenyl, 4-methoxyphenyl, 2-chlorophenyl, 2-naphthyl and the like.
The synthesis method of the chiral silicon-containing polyester takes a complex of copper and a bisoxazoline ligand as a catalyst, and the chiral silicon-containing polyester is prepared by catalyzing enantioselective insertion polymerization of a monomer I (diazo compound) and a monomer II (silane);
the molar ratio of the copper bisoxazoline ligand complex to the monomer I or the monomer II is as follows: 0.005-0.050: 1, preferably 0.010-0.030: 1, more preferably 0.010-0.020: 1; the molar ratio of the monomer II to the monomer III is 1: 1-1: 1.2, preferably 1: 1;
the specific reaction formula is as follows:
in the formula: r 1 And R 2 All of which are aryl groups, and preferably aryl groups having various substituents, such as phenyl, 4-fluorophenyl, 4-methoxyphenyl, 2-chlorophenyl, 2-naphthyl and the like.
Based on the above technical scheme, preferably, R is 1 And R 2 Aryl groups having different substituents are preferred.
Based on the technical scheme, the reaction temperature is preferably-20-80 ℃, and preferably 0-40 ℃.
Based on the technical scheme, the reaction time is preferably 24-48 hours.
Based on the above technical scheme, preferably, the method for synthesizing the chiral silicon-containing polyester comprises the following steps:
under the protection of nitrogen, adding a monomer I and a monomer II into the catalyst solution for reaction to obtain the chiral silicon-containing polyester;
the catalyst solution is formed by dissolving the catalyst in an organic solvent.
Based on the technical scheme, preferably, after the reaction is finished, removing the organic solvent, adding dichloromethane to dissolve the product, dropwise adding cold methanol to separate out the product, removing the upper-layer organic solvent, and performing suction drying to obtain the chiral silicon-containing polyester.
Based on the above technical scheme, the method for removing the organic solvent is preferably to remove the solvent under reduced pressure.
Based on the above technical scheme, preferably, the organic solvent used in the insertion polymerization reaction is selected from Mesitylene (Mesitylene), chlorobenzene (PhCl), chloroform (CHCl) 3 ) Dichloromethane (DCM), tert-butyl methyl ether(s) ((s)) t BME), acetonitrile (MeCN), Tetrahydrofuran (THF), preferably chlorobenzene.
Based on the technical scheme, preferably, the copper bisoxazoline ligand complex is obtained by stirring and reacting a copper precursor and a bisoxazoline ligand in an organic solvent, wherein the reaction temperature is 20-40 ℃, and the reaction time is two hours.
Based on the technical scheme, preferably, the copper precursor is copper (II) trifluoromethanesulfonate (Cu) (OTf) 2 Copper (I) tetraacetonitrile tetrafluoroborate Cu (MeCN) 4 BF 4 Copper cyclohexylbutyrate (II) CuR 2 Copper (I) tetraethyl hexafluorophosphate (Cu) (MeCN) 4 PF 6 Preferably copper (II) trifluoromethanesulfonate (Cu (OTf) 2 。
Based on the above technical scheme, preferably, the bisoxazoline ligand is at least one of L1-L5, preferably L1, and the structural formula of L1-L5 is as follows:
based on the above technical scheme, the molar ratio of the copper precursor to the bisoxazoline ligand is preferably 1:1.0 to 1:1.5, and preferably 1: 1.2.
Based on the above technical scheme, preferably, the organic solvent used by the copper bisoxazoline ligand complex is selected from Mesitylene (Mesitylene), chlorobenzene (PhCl), chloroform (CHCl) 3 ) Dichloromethane (DCM), tert-butyl methyl ether(s) ((s)) t BME), acetonitrile (MeCN), Tetrahydrofuran (THF), preferably chlorobenzene.
Based on the above technical solution, preferably, the organic solvent used in the insertion polymerization reaction is the same as the organic solvent used for the copper bisoxazoline ligand complex.
Based on the technical scheme, preferably, the concentrations of the monomer I and the monomer II in the catalyst solution are respectively 0.1-1.0 mmol/mL.
As a preferred technical scheme, the optical purity characterization step of the polymer is as follows:
the chiral polyester (80mg), toluene (3mL), and diisopropylaluminum hydride toluene solution (0.5mL,1.5M) were added to a reaction flask, the mixture was stirred at-78 ℃ for 0.5 hour, then gradually warmed to room temperature for further reaction for 3 hours, the target diol was isolated, the structure was confirmed by nuclear magnetic resonance, and the optical purity was confirmed by HPLC.
The invention relates to a method for preparing chiral polyester by using a bisoxazoline ligand complex of cheap metal copper as a catalyst to catalyze enantioselective insertion polymerization of a diazo compound (monomer I) and silane (monomer II).
1. High reactivity, and the maximum number average molecular weight of the chiral silicon-containing polyester is 1.42 multiplied by 10 4 ；
2. The reaction stereoselectivity is high, the enantioselectivity can reach 99.2 percent, and the diastereoselectivity can reach 9.1: 1;
3. the chiral silicon-containing polyester has high optical purity and good thermal stability;
4. the catalyst is commercially available, and the reaction operation is simple and practical;
5. the reaction condition is mild, and the substrate range is wide.
Detailed Description
The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
The term "aryl" as used herein, alone or in combination, refers to an optionally substituted aromatic hydrocarbon group having from 6 to about 20, such as from 6 to 12 or from 6 to 10 ring-forming carbon atoms, which may be a monocyclic aryl group, a bicyclic aryl group, or a higher ring aryl group. The bicyclic aryl or higher ring aryl may be a monocyclic aryl with other independent rings such as alicyclic, heterocyclic, aromatic ring, aromatic heterocyclic or higher ring aryl. Non-limiting examples of monocyclic aryl groups include monocyclic aryl groups of 6 to about 12, 6 to about 10, or 6 to about 8 ring-forming carbon atoms, such as phenyl; bicyclic aryl such as naphthyl; polycyclic aryl radicals such as phenanthryl, anthracyl, azulenyl.
The precursor of copper used in the invention: copper (II) trifluoromethanesulfonate Cu (OTf) 2 Copper (I) tetraacetonitrile tetrafluoroborate Cu (MeCN) 4 BF 4 Copper cyclohexylbutyrate (II) CuR 2 Copper (I) tetraethyl hexafluorophosphate (Cu) (MeCN) 4 PF 6 Are all purchased through enokay without any processing; the chiral bisoxazoline ligand used: L1-L5 were purchased via carbofuran and did not require any treatment; the acid chlorides used in the synthesis of monomer 1 can be synthesized according to the references (references ten: Teng, y.; Suwanarusk, R.; Ngai, m.h.; Srinivasan, R.; Ong, a.s.m.; Hod, b.; re nia, l.; Chai, c.l.l.l.bioorg. med.chem.lett.2015,25,607-); monomers 2a-d can be synthesized by reference (reference eleven (a) Kim, d.w.; Joung, s.; Kim, j.g.; Chang, s.angelw.chem.int.ed.2015, 54, 14805-; the remaining reagents used, such as carboxylic acid, p-toluenesulfonylazide and dicyclohexylcarbodiimide, and 4-dimethylaminopyridine, etc., were purchased via carbofuran and did not require any treatment; the polymerization reaction uses super-dry solvent such as mesitylene, chlorobenzene, chloroform, dichloromethane, tert-butyl methyl ether, acetonitrile, tetrahydrofuran, etcPurchased via carbofuran and without any treatment.
Examples 1 to 3
Synthesis of diazo monomers 2a-2c
Under nitrogen, add acid chloride (25.0mmol), ethylene glycol (0.620g, 10.0mmol) and dichloromethane (DCM, 20 mL). Triethylamine (2.526g,25.0mmol) was added dropwise to the ice-water bath, and the mixture was warmed to room temperature to react for 17 hours. Ethyl acetate (20mL) was added to the reaction flask, and the mixture was filtered through celite, and the filtrate was collected, the solvent was removed under reduced pressure, and the intermediate diester was purified by silica gel column chromatography.
The intermediate diester (6.7mmol), p-toluenesulfonyl azide (TsN) were added to a reaction flask 3 4.207g, 75% w/w ethyl acetate solution, 16.0mmol) and acetonitrile (MeCN, 15mL), 1, 8-diazabicycloundec-7-ene (DBU, 3.045g,20.0mmol) in acetonitrile (10mL) was added dropwise, reacted at room temperature for 12 hours, the solvent was removed under reduced pressure, and purified by silica gel column chromatography (petroleum ether/ethyl acetate ═ 50/1 to 10/1) to give monomers 2a-2 c.
Examples 4 to 5
Synthesis of diazo monomers 2d and 2e
Carboxylic acid (10.0mmol), ethylene glycol (0.248g,4.0mmol), dicyclohexylcarbodiimide (DCC,2.063g,10.0mmol), 4-dimethylaminopyridine (DMAP,0.100g,0.8mm ol) and dichloromethane (DCM, 15mL) were added to a reaction flask under nitrogen, and the reaction was allowed to warm to 45 ℃ for 13 hours. Ethyl acetate (20mL) was added to the reaction flask, and the mixture was filtered through celite, and the filtrate was collected, and the solvent was removed under reduced pressure and purified by silica gel column chromatography to obtain an intermediate diester.
The intermediate diester (4.0mmol) and p-toluenesulfonylazide (TsN) were added to a reaction flask 3 2.522g, 75% w/w ethyl acetate solution, 9.6mmol) and acetonitrile (MeCN, 15mL), dropwise 1,8-diazabicycloundecen-7-ene (DBU, 1.824g,12.0mmol) in acetonitrile (10mL) was reacted at room temperature for 12 hours, the solvent was removed under reduced pressure, and purified by silica gel column chromatography (petroleum ether/ethyl acetate: 50/1 to 10/1) to give monomers 2d and 2 e.
Examples 6 to 18
Optimization of reaction conditions for copper-catalyzed silicon-hydrogen bond insertion polymerization
In a glove box, a precursor of copper [ Cu ] is added](2 mol% of the substrate), bisoxazoline ligand L (2.4 mol% of the substrate), NaBAr F (2.4 mol% of the amount of the substrate) and a reaction solvent (1.5mL) were added to the reaction flask, and stirred at room temperature for 2 hours. Under the protection of nitrogen, adding the monomer 1a (0.3mmol) and the monomer 2a (0.3mmol), reacting at 20 ℃ for 24 hours, after the polymerization reaction is finished, purifying the polymerization product (chiral silicon-containing polyester) 3a by a precipitation method (dichloromethane/methanol, specifically, 2 ml dichloromethane dissolved product is added after the solvent is removed under reduced pressure, 15ml cold methanol is dripped to separate out the product, the upper layer solvent is removed, and the polymerization product is obtained by pumping.
The chiral silicon-containing polyester 3a (80mg), toluene (3mL), diisopropylaluminum hydride (DIBAL-H) toluene solution (0.5mL,1.5M) were added to a reaction flask, the mixture was stirred at-78 ℃ for 0.5 hour, then gradually warmed to room temperature for further reaction for 3 hours, the target product diol 4a was isolated, the structure was confirmed by nuclear magnetism, the optical purity was confirmed by HPLC, and the optical purity of the polymer was deduced in reverse.
The equations and ligand structures are as follows:
number average molecular weight (M) of the Polymer n ) And molecular weight distribution (PDI) were measured by gel chromatography (GPC), the yields were isolated, and the reaction temperature and solvent type and catalyst to substrate ratio were varied to prepare products of varying molecular weights, as detailed in table 1.
TABLE 1 asymmetric Si-H bond insertion polymerization condition optimization for copper catalyzed carbene a
Examples 18 to 27
Synthesis of chiral silicon-containing polyester 3a-j by insertion polymerization of silicon-hydrogen bond under catalysis of copper
In a glove box, Cu (OTf) 2 (2 mol% of the substrate), bisoxazoline ligand L1 (2.4 mol% of the substrate), NaBAr F (2.4 mol% of the amount of the substrate) and chlorobenzene (1.5mL) were added to the reaction flask and stirred at room temperature for 2 hours. Under the protection of nitrogen, adding a monomer 1(0.3mmol) and a monomer 2(0.3mmol), reacting at 20 ℃ for 24 hours, after the polymerization reaction is finished, purifying a polymerization product (chiral silicon-containing polyester) 3 by a precipitation method (dichloromethane/methanol, specifically, after the solvent is removed under reduced pressure, 2 ml dichloromethane is added to dissolve the product, 15ml cold methanol is added dropwise to separate out the product, the upper layer solvent is removed, and the polymerization product is obtained by pumping.
The chiral silicon-containing polyester 3(80mg), toluene (3mL), diisopropylaluminum hydride (DIBAL-H) toluene solution (0.5mL,1.5M) were added to a reaction flask, the mixture was stirred at-78 ℃ for 0.5 hour, then gradually warmed to room temperature for further reaction for 3 hours, the target product diol 4 was isolated, the structure was determined by nuclear magnetism, the optical purity was determined by HPLC, and the optical purity of the polymer was deduced.
The reaction and substrate structures are as follows:
number average molecular weight (M) of the Polymer n ) And molecular weight distribution (PDI) by gel chromatography (GPC), yields are isolated yields, as detailed in table 2.
TABLE 2 asymmetric silicon-hydrogen bond insertion polymerization substrate development of copper catalyzed carbene a
Examples 28 to 32
Thermal analysis
Thermal stability of chiral silicon-containing polyesters, e.g. temperature at 5% mass decomposition (T) 5 ) And the temperature at which 50% of decomposition occurs (T) 50 ) Glass transition temperature (T) determined by simultaneous thermal analysis (TGA) g ) As determined by Differential Scanning Calorimetry (DSC) and detailed in table 3.
TABLE 3 thermal analysis of chiral silicon-containing polyesters a
Ethane-1,2-diyl bis(2-diazo-2-phenylacetate)(2a):16mmol scale,3.997g,71％overall yield,yellow solid,mp＝82-84℃,new compound,R f ＝0.50(hexanes/ethyl acetate＝30/1). 1 H NMR(400MHz,CDCl 3 )δ7.52-7.43(m,4H),7.42-7.35(m,4H),7.23-7.16(m,2H),4.55 (s,4H). 13 C NMR(100MHz,CDCl 3 )δ165.0,129.2,126.2,125.4,124.2,63.7,62.7. HRMS-ESI Calculated for C 18 H 14 KN 4 O 4 [M+K] + ,389.0647；found,389.0646.
Ethane-1,2-diyl bis(2-diazo-2-(4-fluorophenyl)acetate)(2b):10mmol scale,1.544g, 41％overall yield,yellow solid,mp＝120-122℃,new compound,R f ＝0.60(hexanes/ethyl acetate＝30/1). 1 H NMR(400MHz,CDCl 3 )δ7.55-7.38(m,4H),7.18-7.02(m,4H),4.54(s, 4H). 13 C NMR(100MHz,CDCl 3 )δ165.0,161.3(d, 1 J F-C ＝246.5Hz),126.1(d, 3 J F-C ＝7.9 Hz),121.1(d, 4 J F-C ＝3.3Hz),116.3(d, 2 J F-C ＝21.9Hz),62.9,62.8. 19 F NMR(376MHz, CDCl 3 )δ-115.88.HRMS-ESI Calculated for C 18 H 12 F 2 KN 4 O 4 [M+K] + ,425.0458；found, 425.0455.
Ethane-1,2-diyl bis(2-diazo-2-(naphthalen-2-yl)acetate)(2c):4mmol scale,0.986g, 60％overall yield,yellow solid,mp＝171-173℃,new compound,R f ＝0.40(hexanes/ethyl acetate＝30/1). 1 H NMR(400MHz,CDCl 3 )δ8.00(s,2H),7.89-7.62(m,6H),7.61-7.30(m, 6H),4.63(s,4H). 13 C NMR(100MHz,CDCl 3 )δ165.1,133.8,131.7,128.9,127.8,127.8, 126.8,126.0,122.8,122.5,122.1,64.2,62.8.HRMS-ESI Calculated for C 26 H 18 KN 4 O 4 [M+K] + ,489.0960；found,489.0963.
Ethane-1,2-diyl bis(2-(2-chlorophenyl)-2-diazoacetate)(2d):3.2mmol scale,0.986g, 71％overall yield,yellow solid,mp＝100-102℃,new compound,R f ＝0.40(hexanes/ethyl acetate＝30/1). 1 H NMR(400MHz,CDCl 3 )δ7.60-7.48(m,2H),7.48-7.38(m,2H), 7.38-7.25(m,4H),4.51(s,4H). 13 C NMR(100MHz,CDCl 3 )δ165.4,134.0,132.5,130.2, 129.9,127.4,123.8,62.9.HRMS-ESI Calculated for C 18 H 12 Cl 2 KN 4 O 4 [M+K] + ,456.9867；found,456.9868( 35 Cl+ 35 Cl),458.9840( 35 Cl+ 37 Cl)and 460.9812( 37 Cl+ 37 Cl).
Ethane-1,2-diyl bis(2-diazo-2-(4-methoxyphenyl)acetate)(2e):4mmol scale,0.811g, 49％overall yield,yellow solid,mp＝125-127℃,new compound,R f ＝0.50(hexanes/ethyl acetate＝10/1). 1 H NMR(400MHz,CDCl 3 )δ7.44-7.31(m,4H),7.01-6.89(m,4H),4.53(s, 4H),3.81(s,6H). 13 C NMR(100MHz,CDCl 3 )δ165.5,158.3,126.2,116.7,114.8,62.8,62.7, 55.5.HRMS-ESI Calculated for C 20 H 18 KN 4 O 6 [M+K] + ,449.0858；found,449.0858.
Polyester(±)-3a:451mg,92％yield,white foamy solid,new compound. 1 H NMR(400 MHz,CDCl 3 )δ7.85-7.24(m,4H),7.24-7.04(m,10H),4.35-3.73(m,4H),3.66-3.49(m,2H), 0.47-0.21(m,12H). 13 C NMR(100MHz,CDCl 3 )δ172.4,137.0,135.7,133.3,133.0,129.4, 128.8,128.5,128.2,127.4,126.0,125.9,63.1,62.5,62.2,62.1,47.4,45.9,41.3,0.2,-4.1,-4.2, -6.8.
Polyester(-)-3a:113mg,77％yield,pale yellow solid,new compound,[α] 20 D ＝-18.87(c 0.80,THF). 1 H NMR(400MHz,CDCl 3 )δ7.47-7.28(m,2H),7.23-7.11(m,12H),4.19-3.92 (m,4H),3.63-3.52(m,2H),0.35-0.23(m,12H). 13 C NMR(100MHz,CDCl 3 )δ172.5,172.4, 137.6,137.1,137.0,135.7,135.7,133.4,133.4,133.3,132.3,129.4,128.8,128.5,128.4, 128.4,128.3,128.2,126.1,126.0,125.9,62.2,47.4,46.1,46.0,45.9,1.0,-3.7,-4.1,-4.1,-4.2, -4.4,-4.7,-6.8.
Polyester(-)-3b:133mg,85％yield,pale yellow solid,new compound,[α] 20 D ＝-29.39(c 0.82,THF). 1 H NMR(400MHz,CDCl 3 )δ7.56-7.19(m,4H),7.16-7.00(m,4H),6.98-6.78 (m,4H),4.34-3.86(m,4H),3.65-3.47(m,2H),0.36-0.19(m,12H). 13 C NMR(100MHz, CDCl 3 )δ172.3,161.3(d, 1 J F-C ＝244.4Hz),136.9,136.8,133.5,133.4,133.3,133.0,131.4 (d, 4 J F-C ＝2.9Hz),129.9(d, 3 J F-C ＝7.5Hz),115.3,115.3,115.0(d, 2 J F-C ＝21.1Hz),63.1, 62.2,62.2,46.5,45.2,45.1,45.0,-3.8,-4.1,-4.2,-4.2,-4.3,-4.4,-6.9. 19 F NMR(376MHz, CDCl 3 )δ-117.16,-117.22,-117.24,-117.28,-117.34,-117.38,-117.44.
Polyester(-)-3c:166mg,94％yield,pale yellow solid,new compound,[α] 20 D ＝-52.60(c 0.96,THF). 1 H NMR(400MHz,CDCl 3 )δ7.97-7.49(m,9H),7.48-7.29(m,5H),7.23-7.17 (m,4H),4.26-3.88(m,4H),3.80-3.63(m,2H),0.39-0.15(m,12H). 13 C NMR(100MHz, CDCl 3 )δ172.4,137.0,133.5,133.5,133.4,133.3,131.9,127.8,127.7,127.6,127.6,127.4, 126.5,126.0,125.4,62.2,46.0,-4.1,-4.2.
Polyester(-)-3d:148mg,89％yield,white solid,new compound,[α] 20 D ＝-76.57(c 0.70, THF). 1 H NMR(400MHz,CDCl 3 )δ7.69-7.48(m,2H),7.37-7.21(m,6H),7.15(t,J＝7.4 Hz,2H),7.06(t,J＝7.3Hz,2H),4.57-4.30(m,2H),4.28-3.86(m,4H),0.43-0.19(m,12H). 13 C NMR(100MHz,CDCl 3 )δ171.8,136.9,136.8,133.9,133.8,133.5,133.3,133.0,133.0, 130.6,130.4,130.3,129.9,129.6,129.4,128.8,127.2,127.2,127.1,126.8,126.6,63.2,62.4, 62.3,42.1,40.7,-3.3,-3.3,-4.2,-4.2,-4.3,-4.3,-5.2,-6.8.
Polyester(-)-3e:172mg,91％yield,pale yellow solid,new compound,[α] 20 D ＝-61.25(c 0.64,THF). 1 H NMR(400MHz,CDCl 3 )δ7.76-7.60(m,2H),7.57-7.27(m,10H),7.23-7.04 (m,4H),4.64-4.35(m,2H),4.26-3.94(m,4H),0.58-0.24(m,12H). 13 C NMR(100MHz, CDCl 3 )δ172.0,142.1,134.8,134.2,133.9,133.0,130.5,129.4,127.1,126.6,126.5,62.4, 40.9,-3.1,-4.2,-4.2.
Polyester(-)-3f:113mg,68％yield,pale yellow solid,new compound,[α] 20 D ＝-56.87(c 0.64,THF). 1 H NMR(400MHz,CDCl 3 )δ8.02-7.42(m,3H),7.39-6.99(m,9H),4.57-4.32 (m,2H),4.24-3.91(m,4H),0.48-0.17(m,12H). 13 C NMR(100MHz,CDCl 3 )δ172.0,171.9, 140.3,139.8,135.6,135.5,135.4,135.4,135.2,134.1,133.9,132.9,130.5,130.4,130.3, 129.6,129.4,129.3,127.6,127.2,127.1,126.9,126.7,126.6,62.8,62.3,62.2,62.2,40.9,40.8, 40.7,-2.9,-3.4,-4.1,-5.7.
Polyester(-)-3g:144mg,82％yield,pale yellow solid,new compound,[α] 20 D ＝-57.88(c 1.18,THF). 1 H NMR(400MHz,CDCl 3 )δ7.91-7.56(m,2H),7.35-6.91(m,8H),4.79-4.37 (m,2H),4.14-3.59(m,4H),2.55-1.98(m,6H),0.63-0.20(m,12H). 13 C NMR(100MHz, CDCl 3 )δ171.9,140.0,140.0,136.9,135.5,135.4,133.9,133.8,133.1,130.6,130.6,129.9, 129.5,129.3,128.8,127.0,126.8,126.6,126.5,62.1,62.1,62.0,62.0,40.6,40.5,23.0,-1.9.
Polyester(+)-3h:169mg,91％yield,pale yellow solid,new compound,[α] 20 D ＝+4.19(c 0.62,THF). 1 H NMR(400MHz,CDCl 3 )δ7.52(d,J＝6.4Hz,4H),7.41(d,J＝6.3Hz,4H), 7.12(d,J＝6.7Hz,4H),6.76(d,J＝7.4Hz,4H),4.36-3.89(m,4H),3.84-3.69(m,6H), 3.67-3.52(m,2H),0.47-0.20(m,12H). 13 C NMR(100MHz,CDCl 3 )δ172.8,157.9,142.0, 134.8,134.7,129.6,127.7,126.5,113.7,62.2,55.4,44.9,-3.8,-4.1.
Polyester(+)-3i:138mg,83％yield,pale yellow solid,new compound,[α] 20 D ＝+6.71(c 0.70,THF). 1 H NMR(400MHz,CDCl 3 )δ7.59-7.31(m,8H),7.28-7.06(m,10H),4.35-3.91 (m,4H),3.73-3.52(m,2H),0.46-0.16(m,12H). 13 C NMR(100MHz,CDCl 3 )δ172.5,142.0, 135.8,134.8,134.5,128.5,128.3,126.5,125.9,62.2,46.0,-3.9,-4.2.
Polyester(+)-3j:138mg,63％yield,pale green solid,new compound,[α] 20 D ＝+7.17(c 1.20,THF). 1 H NMR(400MHz,CDCl 3 )δ7.56-7.28(m,4H),7.16-7.02(m,4H),4.13-3.90 (m,4H),3.67-3.38(m,2H),1.10(t,J＝7.0Hz,6H),0.37-0.22(m,12H). 13 C NMR(100MHz, CDCl 3 )δ172.7,137.5,133.5,133.5,133.4,133.3,133.2,128.2,60.5,60.3,45.7,45.6,45.5, 14.4,14.3,-3.7,-3.7,-3.7,-3.8,-3.8,-3.9,-3.9,-4.0,-4.5,-4.5.
2,2'-(1,4-Phenylenebis(dimethylsilanediyl))bis(2-phenylethan-1-ol)(4a):83mg(104 mg polymer 3a was used),89％yield,white solid,mp＝95-96℃,new compound,99.1％ee, 9.0:1dl/meso,[α] 20 D ＝+51.25(c 1.04,THF),R f ＝0.30(hexanes/ethyl acetate＝3/1). 1 H NMR(400MHz,CDCl 3 )δ7.41-7.33(m,4H),7.28-7.24(m,4H),7.20-7.12(m,2H), 7.07-6.96(m,4H),4.09(t,J＝11.2,2H),4.01-3.88(m,2H),2.66(dd,J＝11.3,4.4Hz,2H), 1.35(brs,2H),0.26(s,6H),0.23(s,6H). 13 C NMR(100MHz,CDCl 3 )δ140.0,138.1,133.4, 128.7,128.3,125.6,63.2,41.6,-3.7,-4.8.HPLC:Chiracel OD-3 column,230nm,30℃, n-Hexane/i-PrOH＝85/15,flow＝0.8mL/min,retention time 19.7min,22.1min(meso)and 24.3min(major).HRMS:Calculated for C 26 H 38 NO 2 Si 2 [M+NH 4 ] + 452.2436,found: 452.2432.
2,2'-(1,4-Phenylenebis(dimethylsilanediyl))bis(2-(4-fluorophenyl)ethan-1-ol)(4b):60 mg,83％yield,colorless viscous liquid,new compound,98.9％ee,8.0:1dl/meso,[α] 20 D ＝+47.76(c 1.16,THF),R f ＝0.45(hexanes/ethyl acetate＝3/1). 1 H NMR(400MHz,CDCl 3 ) δ7.41-7.29(m,4H),7.03-6.87(m,8H),4.01(t,J＝11.1Hz,2H),3.92(dd,J＝11.3,4.5Hz, 2H),2.62(dd,J＝11.0,4.5Hz,2H),1.44(brs,2H),0.26(s,6H),0.24(s,6H). 13 C NMR(100 MHz,CDCl 3 )δ161.1(d, 1 J F-C ＝243.4Hz),138.0,135.7(d, 4 J F-C ＝2.8Hz),133.4,129.4(d, 3 J F-C ＝7.5Hz),115.5(d, 2 J F-C ＝21.1Hz),63.3,40.7,-3.8,-4.8. 19 F NMR(376MHz,CDCl 3 ) δ-117.99.HPLC:Chiracel OD-H column,230nm,30℃,n-Hexane/i-PrOH＝93/7,flow＝ 0.8mL/min,retention time 22.8min(major),25.7min(meso)and 31.2min.HRMS: Calculated for C 26 H 36 F 2 NO 2 Si 2 [M+NH 4 ] + 488.2247,found:488.2247.
2,2'-(1,4-Phenylenebis(dimethylsilanediyl))bis(2-(naphthalen-1-yl)ethan-1-ol)(4c):70 mg,96％yield,colorless viscous liquid,new compound,99.2％ee,9.1:1dl/meso,[α] 20 D ＝ +41.71(c 1.34,THF),R f ＝0.20(hexanes/ethyl acetate＝3/1). 1 H NMR(400MHz,CDCl 3 )δ 7.81(d,J＝7.5Hz,2H),7.77-7.67(m,4H),7.50-7.36(m,10H),7.16(dd,J＝8.4,1.8Hz, 2H),4.20(t,J＝11.3Hz,2H),4.02(dd,J＝11.4,4.4Hz,2H),2.85(dd,J＝11.3,4.4Hz,2H), 1.52(brs,2H),0.30(s,6H),0.28(s,6H). 13 C NMR(100MHz,CDCl 3 )δ138.1,137.7,133.8, 133.5,131.9,128.3,127.8,127.5,127.2,126.2,126.2,125.2,63.2,41.8,-3.6,-4.7.HPLC: Chiracel OD-H column,230nm,30℃,n-Hexane/i-PrOH＝60/40,flow＝0.7mL/min, retention time 16.0min,20.3min(meso)and 26.8min(major).HRMS:Calculated for C 34 H 42 NO 2 Si 2 [M+NH 4 ] + 552.2749,found:552.2746.
2,2'-(1,4-Phenylenebis(dimethylsilanediyl))bis(2-(2-chlorophenyl)ethan-1-ol)(4d):60 mg,83％yield,colorless viscous liquid,new compound,98.0％ee,6.0:1dl/meso,[α] 20 D ＝ -22.92(c 1.20,THF),R f ＝0.40(hexanes/ethyl acetate＝3/1). 1 H NMR(400MHz,CDCl 3 )δ 7.47-7.40(m,4H),7.39-7.35(m,2H),7.24-7.15(m,2H),7.13-7.03(m,4H),4.07-3.91(m, 4H),3.41(dd,J＝10.6,5.0Hz,2H),1.34(brs,2H),0.29(s,6H),0.27(s,6H). 13 C NMR(100 MHz,CDCl 3 )δ138.5,138.0,134.8,133.5,130.0,127.6,127.1,126.5,63.4,36.7,-3.4,-5.1. HPLC:Chiracel OD-H column,230nm,30℃,n-Hexane/i-PrOH＝90/10,flow＝0.9 mL/min,retention time 20.2min,23.2min(meso)and 26.4min(major).HRMS:Calculated for C 26 H 36 Cl 2 NO 2 Si 2 [M+NH 4 ] + 520.1656,found:520.1653( 35 Cl+ 35 Cl),522.1627( 35 Cl+ 37 Cl) and 524.1609( 37 Cl+ 37 Cl).
2,2'-([1,1'-Biphenyl]-4,4'-diylbis(dimethylsilanediyl))bis(2-(2-chlorophenyl)ethan-1-ol) (4e):62mg,85％yield,colorless viscous liquid,new compound,97.4％ee,5.6:1dl/meso, [α] 20 D ＝-25.34(c 1.18,THF),R f ＝0.20(hexanes/ethyl acetate＝3/1). 1 H NMR(400MHz, CDCl 3 )δ7.63(d,J＝8.0Hz,4H),7.56(d,J＝8.0Hz,4H),7.42-7.36(m,2H),7.23-7.17(m, 2H),7.13-7.05(m,4H),4.11-3.97(m,4H),3.45(dd,J＝10.5,5.1Hz,2H),1.47(brs,2H), 0.33(s,6H),0.31(s,6H). 13 C NMR(100MHz,CDCl 3 )δ141.9,138.5,135.8,134.8,134.7, 130.0,127.6,127.0,126.6,126.5,63.3,36.7,-3.2,-5.0.HPLC:Chiracel AD-H column,230 nm,30℃,n-Hexane/i-PrOH＝75/25,flow＝0.9mL/min,retention time 9.8min(major), 13.1min(meso)and 15.6min.HRMS:Calculated for C 32 H 40 Cl 2 NO 2 Si 2 [M+NH 4 ] + 596.1969, found:596.1972( 35 Cl+ 35 Cl),598.1950( 35 Cl+ 37 Cl)and 600.1940( 37 Cl+ 37 Cl).
2,2'-(1,3-Phenylenebis(dimethylsilanediyl))bis(2-(2-chlorophenyl)ethan-1-ol)(4f):62 mg,86％yield,colorless viscous liquid,new compound,98.4％ee,5.5:1dl/meso,[α] 20 D ＝ -11.81(c 1.16,THF),R f ＝0.40(hexanes/ethyl acetate＝3/1). 1 H NMR(400MHz,CDCl 3 )δ 7.55-7.44(m,3H),7.41-7.30(m,3H),7.22-7.13(m,2H),7.12-6.96(m,4H),4.06-3.85(m, 4H),3.37(dd,J＝10.4,5.2Hz,2H),1.59(brs,2H),0.27(s,12H). 13 C NMR(100MHz, CDCl 3 )δ139.8,138.6,135.9,135.2,134.7,130.0,127.6,127.3,127.0,126.4,63.3,36.7,-3.3, -3.4,-4.9,-4.9.HPLC:Chiracel AD-H column,230nm,30℃,n-Hexane/i-PrOH＝90/10, flow＝0.8mL/min,retention time 15.6min(major),17.3min(meso)and 23.2min.HRMS: Calculated for C 26 H 36 Cl 2 NO 2 Si 2 [M+NH 4 ] + 520.1656,found:520.1657( 35 Cl+ 35 Cl),522.1630 ( 35 Cl+ 37 Cl)and 524.1603( 37 Cl+ 37 Cl).
2,2'-((2,5-Dimethyl-1,4-phenylene)bis(dimethylsilanediyl))bis(2-(2-chlorophenyl)ethan -1-ol)(4g):68mg,94％yield,colorless viscous liquid,new compound,94.9％ee,4.0:1 dl/meso,[α] 20 D ＝+3.60(c 1.36,THF),R f ＝0.40(hexanes/ethyl acetate＝3/1). 1 H NMR(400 MHz,CDCl 3 )δ7.38(dd,J＝7.9,1.2Hz,2H),7.25-7.06(m,8H),4.04(t,J＝11.1Hz,2H), 3.88(dd,J＝11.3,4.6Hz,2H),3.60-3.48(m,2H),2.39(s,6H),1.43(br,2H),0.36(s,6H), 0.27(s,6H). 13 C NMR(100MHz,CDCl 3 )δ140.1,138.6,136.9,136.6,134.8,130.0,127.8, 127.0,126.4,63.3,36.4,23.2,-1.9,-2.0,-3.1,-3.1.HPLC:Chiracel AD-H column,230nm, 30℃,n-Hexane/i-PrOH＝85/15,flow＝0.9mL/min,retention time 7.3min(major),8.8min (meso)and 10.7min.HRMS:Calculated for C 28 H 40 Cl 2 NO 2 Si 2 [M+NH 4 ] + 548.1969,found: 548.1968( 35 Cl+ 35 Cl),550.1942( 35 Cl+ 37 Cl),552.1928( 37 Cl+ 37 Cl).
2,2'-([1,1'-Biphenyl]-4,4'-diylbis(dimethylsilanediyl))bis(2-(4-methoxyphenyl)ethan-1- ol)(4h):67mg,92％yield,colorless viscous liquid,new compound,98.4％ee,5.6:1dl/meso, [α] 20 D ＝+27.54(c 1.22,THF),R f ＝0.20(hexanes/ethyl acetate＝3/1). 1 H NMR(400MHz, CDCl 3 )δ7.60(d,J＝8.1Hz,4H),7.50(d,J＝8.1Hz,4H),6.97(d,J＝8.7Hz,4H), 6.87-6.78(m,4H),4.05(t,J＝11.2Hz,2H),3.96(dd,J＝11.2,4.5Hz,2H),3.79(s,6H), 2.63(dd,J＝11.2,4.6Hz,2H),1.52(brs,2H),0.30(s,6H),0.27(s,6H). 13 C NMR(100MHz, CDCl 3 )δ157.6,141.8,136.1,134.7,131.7,129.2,126.5,114.2,63.4,55.4,40.5,-3.5,-4.7. HPLC:Chiracel IA column,230nm,30℃,n-Hexane/i-PrOH＝65/35,flow＝0.7mL/min, retention time 14.8min(major),20.3min(meso)and 22.7min.HRMS:Calculated for C 34 H 46 NO 4 Si 2 [M+NH 4 ] + 588.2960,found:588.2964.
2,2'-([1,1'-Biphenyl]-4,4'-diylbis(dimethylsilanediyl))bis(2-phenylethan-1-ol)(4i):69 mg,96％yield,white solid,mp＝76-78℃,new compound,99.0％ee,7.2:1dl/meso,[α] 20 D ＝ +36.47(c 1.36,THF),R f ＝0.30(hexanes/ethyl acetate＝3/1). 1 H NMR(400MHz,CDCl 3 )δ 7.58(d,J＝8.1Hz,4H),7.48(d,J＝8.1Hz,4H),7.27-7.22(m,4H),7.17-7.10(m,2H), 7.09-6.98(m,4H),4.10(t,J＝11.3Hz,2H),3.96(dd,J＝11.3,4.4Hz,2H),2.68(dd,J＝ 11.2,4.5Hz,2H),1.46(brs,2H),0.29(s,6H),0.25(s,6H). 13 C NMR(100MHz,CDCl 3 )δ 141.8,140.0,135.9,134.7,128.7,128.3,126.6,125.6,63.3,41.7,-3.5,-4.7.HPLC:Chiracel AD-H column,230nm,30℃,n-Hexane/i-PrOH＝70/30,flow＝0.9mL/min,retention time 9.4min(major),16.0min and 18.4min(meso).HRMS:Calculated for C 32 H 42 NO 2 Si 2 [M+NH 4 ] + 528.2749,found:528.2751。
Claims (6)
1. A chiral silicon-containing polyester, characterized in that: the chiral silicon-containing polyester has a structure shown as a general formula III:
in the formula: r is 1 And R 2 Are all aryl groups.
2. A method for synthesizing the chiral silicon-containing polyester of claim 1, which is characterized in that: catalyzing enantioselective insertion polymerization of a monomer I and a monomer II by using a copper bisoxazoline ligand complex as a catalyst to prepare the chiral silicon-containing polyester;
the molar ratio of the copper bisoxazoline ligand complex to the monomer I or the monomer II is 0.005-0.050: 1; the molar ratio of the monomer I to the monomer II is 1: 1-1: 1.2;
the specific reaction formula is as follows:
in the formula: r 1 And R 2 Are both aryl;
the copper bisoxazoline ligand complex is obtained by stirring and reacting a copper precursor and a bisoxazoline ligand in an organic solvent;
the precursor of the copper is at least one of copper trifluoromethanesulfonate (II), copper tetrafluoborate (I), copper cyclohexylbutyrate (II) and copper tetrafluophosphate (I);
the bisoxazoline ligand is at least one of L1-L5; the structural formula of the L1-L5 is as follows:
3. the method of claim 2, wherein: the reaction temperature is-20 to 80 ℃; the reaction time is 12-48 h.
4. The method of claim 2, wherein: the method comprises the following steps:
under the protection of nitrogen, adding a monomer I and a monomer II into the catalyst solution, and reacting at-20-80 ℃ for 12-48h to obtain the chiral silicon-containing polyester;
the catalyst solution is formed by dissolving the catalyst in an organic solvent.
5. The method of claim 4, wherein: the organic solvent is at least one of mesitylene, chlorobenzene, chloroform, dichloromethane, tert-butyl methyl ether, acetonitrile and tetrahydrofuran.
6. The method of claim 4, characterized by: the concentration of the monomer I and the monomer II in the catalyst solution is 0.1-1.0 mmol/mL respectively.
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| US5298623A (en) * | 1991-11-08 | 1994-03-29 | Massachusetts Institute Of Technology | Cu complexes of bis-oxazolines and their use |
| US5563230A (en) * | 1994-09-09 | 1996-10-08 | National Science Council | Chiral smectic liquid crystalline polymers |
| CN1252078A (en) * | 1997-02-06 | 2000-05-03 | Basf公司 | Chinrally nematic polyesters |
| CN1384105A (en) * | 2001-04-27 | 2002-12-11 | 住友化学工业株式会社 | Asymmetric copper compound and cyclopropanation reaction with it |
| CN1594397A (en) * | 2004-06-17 | 2005-03-16 | 武汉化工学院 | Heterochain polymer chiral stationary phase and process for preparing same |
| CN1626524A (en) * | 2003-12-08 | 2005-06-15 | 北京大学 | Dual functions ligand compound of chirality dioxazoline, preparation and application |
| JP2005255593A (en) * | 2004-03-10 | 2005-09-22 | Nagoya Kogyo Univ | Methods for producing optically active oxazoline compound, optically active transition metal complex and asymmetric diels-alder reaction product |
| CN104086773A (en) * | 2014-07-04 | 2014-10-08 | 苏州大学 | Chiral polysilsesquioxane containing arylidene in skeleton and preparation method and application thereof |
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| US5298623A (en) * | 1991-11-08 | 1994-03-29 | Massachusetts Institute Of Technology | Cu complexes of bis-oxazolines and their use |
| US5563230A (en) * | 1994-09-09 | 1996-10-08 | National Science Council | Chiral smectic liquid crystalline polymers |
| CN1252078A (en) * | 1997-02-06 | 2000-05-03 | Basf公司 | Chinrally nematic polyesters |
| CN1384105A (en) * | 2001-04-27 | 2002-12-11 | 住友化学工业株式会社 | Asymmetric copper compound and cyclopropanation reaction with it |
| CN1626524A (en) * | 2003-12-08 | 2005-06-15 | 北京大学 | Dual functions ligand compound of chirality dioxazoline, preparation and application |
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