CN114907231B - Indene chiral spiro fluorescent compound, and preparation method and application thereof - Google Patents

Indene chiral spiro fluorescent compound, and preparation method and application thereof Download PDF

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CN114907231B
CN114907231B CN202210714297.2A CN202210714297A CN114907231B CN 114907231 B CN114907231 B CN 114907231B CN 202210714297 A CN202210714297 A CN 202210714297A CN 114907231 B CN114907231 B CN 114907231B
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indene
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崔玉明
徐利文
韩路路
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Hangzhou Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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Abstract

The invention relates to an indene chiral spiro fluorescent compound, and a preparation method and application thereof. The structural formula of the chiral indene derivative is shown as formula (1). The method comprises the steps of taking a complex formed by palladium salt and chiral ligand as a catalyst precursor, taking 2-arylcyclohex-2-ene-1-ketoxime ether and diaryl acetylene as reactants, and carrying out asymmetric functionalization on carbon-hydrogen bonds in the reactants in a reaction medium in the presence of an oxidant to obtain the compound; the method has good adaptability to aryl compounds and diaryl acetylenes containing substituent groups with different properties, has simple synthesis method, and cheap and easily available ligand, and can obtain a series of indene chiral spiro fluorescent compounds with moderate to excellent yield and enantioselectivity. The invention uses the rigid skeleton structure of indene spiro, so that the chiral stability of the indene spiro in an excited state can be kept very good, and the high luminous efficiency can be obtained, thus the indene spiro has wide application prospect in the field of chiral organic luminescent materials.

Description

Indene chiral spiro fluorescent compound, and preparation method and application thereof
Technical Field
The invention belongs to the field of organic luminescent material chemistry, and relates to an indene chiral spiro fluorescent compound, and a preparation method and application thereof.
Background
The chiral fluorescent compound has important application value in the fields of chiral recognition and resolution, pharmaceutical chemistry, material science, food detection, life science and the like, so the synthesis and functional research of the chiral fluorescent compound are attracting attention in recent years. One of the main problems faced by the research of chiral fluorescent materials is that the synthesis method of chiral fluorescent compounds is limited in ten minutes. On the one hand, chiral fluorescent compounds with high optical purity are usually prepared by taking chiral source compounds as raw materials through multi-step reaction, so that the reaction efficiency is low and the economy is poor. On the other hand, although the chiral proliferation effect can be maximally volatilized by the asymmetric catalytic synthesis technology, the optical purity and fluorescence properties of the obtained target compound are often not ideal enough, so that the development of catalytic synthesis and application research of chiral fluorescent molecules is urgent. The spiro compound based on the indene structural unit is a kind of organic micromolecules with stronger rigidity, can keep the stability of the spiro compound under an excited state, is favorable for obtaining higher quantum yield, and is further introduced with a proper chromophore to be hopeful to obtain chiral fluorescent materials with different emission wavelengths. It has been reported in the literature that asymmetric cyclization of substituted aromatic hydrocarbons with alkynes in the presence of a suitable chiral catalyst can efficiently construct indene chiral spiro compounds of corresponding structures, such as Hon Wai Lam (S.R.Chidipudi, D.J.Burns, I.Khan, H.W. Lam, angew.Chem., int.Ed.2015,54, 13975-13979), book-moving force (J.zheng, S. -B.Wang, C.zheng, S. -L.You, J.Am.Chem.Soc.2015,137,4880-4883) and the like, which are all achieved by using chiral cyclopentadienyl rhodium complex catalysts and Luan Xinjun and the like (L.Yang, H.Zheng, L.Luo, J.nan, J.Liu, Y.Wang, X.Luan, J.Am.Chem.Soc.2015,137,4876-4879) and chiral aza-carbene palladium catalysts. The disadvantage is that the chiral ligand with higher cost is used in the research, and the development of a more economic and efficient synthetic strategy of the indene chiral spiro fluorescent compound is of great significance.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides an indene spiro chiral fluorescent compound.
The indene chiral spiro fluorescent compound provided by the invention has a structural formula (1) as follows:
wherein R is 1 、R 2 Any one selected from hydrogen, alkyl or aryl; r is R 3 Selected from any one of hydrogen, trifluoromethyl, alkoxy, aryl or halogen.
Preferably, the indene chiral spiro fluorescent compound has a structural formula of any one of the compounds shown in the following formulas a to p:
the second object of the invention is to provide a method for synthesizing indene chiral spiro fluorescent compounds.
The method comprises the following steps: 2-aryl cyclohex-2-ene-1-ketoxime ether with a structural formula shown in formula (2) and diaryl acetylene with a structural formula shown in formula (3) are used as reactants, a complex formed by palladium salt and chiral ligand is used as a catalyst precursor, the reaction is carried out in a reaction medium and air at 40-90 ℃ for 10-48h in the presence of an oxidant, and after the reaction is finished, a product is separated by a conventional separation method, so that the indene chiral spiro compound is obtained; the synthetic route is as follows:
the chiral ligand is N-single protective chiral amino acid and comprises any one of Boc-D-valine (Boc-D-Val-OH), boc-L-isoleucine (Boc-lle-OH), boc-L-phenylalanine (Boc-Phe-OH), N-Boc-L-tertiary leucinine (Boc-L-TLEOH), N-acetyl-L-alanine (N-Ac-L-Ala-OH), N-benzyloxycarbonyl-L-valine (N-CBZ-L-Val-OH), N-benzyloxycarbonyl-L-phenylalanine (CBZ-L-Phe-OH) and N-acetyl-L-leucine (N-Ac-L-Leu-OH), and the structural formulas of the chiral ligand are shown in the following respectively:
preferably, the palladium salt is any one or more of palladium chloride, palladium acetate, palladium trifluoroacetate and palladium tetrafluoroborate tetraacetonitrile.
Preferably, the oxidant is one or more of silver acetate, silver oxide, silver carbonate and p-benzoquinone.
Preferably, the reaction medium is any one or a mixture of more of methanol, tertaol, tetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane, acetic acid and acetone.
Preferably, the molar concentration of the 2-arylcyclohex-2-en-1-one oxime ether in the reaction solution is 0.25 to 1mol/L; the amount of the diaryl acetylene is 110 to 300mol% of the 2-aryl cyclohex-2-en-1-one oxime ether.
Preferably, the palladium salt is used in an amount of 1 to 10mol% of 2-arylcyclohex-2-en-1-one oxime ether; the dosage of the chiral ligand is 2-20mol% of 2-aryl cyclohex-2-ene-1-ketoxime ether; the usage amount of the oxidant is 100-300 mol% of 2-aryl cyclohex-2-en-1-one oxime ether.
The third object of the invention is to provide the application of the indene chiral spiro fluorescent compound as a chiral organic luminescent material.
Compared with the prior art, the invention has the following beneficial effects:
(1) The palladium salt catalyst and the N-single-protection hand-protecting amino acid ligand used in the preparation method are both commercial reagents, and are low in cost and easy to obtain.
(2) The preparation method provided by the invention has high enantioselectivity, can obtain indene chiral spiro fluorescent compounds with moderate to excellent yield, and has higher fluorescence quantum yield.
(3) The preparation method of the invention does not need to isolate air, has convenient operation, simple post-treatment and purification and easy amplification synthesis.
Drawings
FIG. 1 shows fluorescence emission spectra of reaction products a-e in examples 1-5.
FIGS. 2-6 show UV absorption spectra of reaction products a-e in examples 1-5, respectively.
Detailed Description
As described above, in view of the shortcomings of the prior art, the present inventors have long studied and practiced a lot, and have proposed the technical solution of the present invention, which mainly comprises: (1) The reaction of the invention does not need to isolate oxygen, can be carried out in an air environment, palladium salt and chiral ligand form a palladium complex catalyst in situ, activate aryl C-H bond and then sequentially carry out asymmetric cyclization reaction on C≡ C, C =C transfer insertion to obtain a required product; the method has good adaptability to substrates containing substituents with different properties, and can obtain a series of indene chiral spiro fluorescent compounds with moderate to excellent yield and enantioselectivity. (2) The invention uses the rigid skeleton structure of indene spiro, so that the chiral stability of the indene spiro in an excited state can be kept very good, and the indene spiro has very high luminous efficiency and fluorescence property, thereby having wide application prospect in the field of chiral organic luminescent materials.
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Example 1
(S, E) -2-methyl-2 ',3' -diphenylspiro [ cyclohexane-1, 1' -cyclopentane [ a ] naphthalene ] -2-en-6-one-O-methyloxime
To a 25mL reaction tube was added (E) -3-methyl-2- (naphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (53 mg,0.2 mmol), diphenylacetylene (39 mg,0.22 mmol), palladium acetate (0.9 mg,0.004 mmol), boc-D-valine (1.7 mg,0.008 mmol), silver oxide (46 mg,0.2 mmol), and further dichloromethane (2 mL), and tertanol (1 mL). The reaction tube was moved to 70℃for 16 hours in an oil bath. The mixture was purified by flash column chromatography to give a yellow solid (79 mg,0.178 mmol) in 89% yield. The fluorescence emission spectrum is shown in fig. 1, and the ultraviolet absorption spectrum is shown in fig. 2.
1 H NMR(400MHz,CDCl 3 )δ7.85-7.77(m,1H),7.73(d,J＝8.4Hz,1H), 7.59(d,J＝8.0Hz,1H),7.45(d,J＝8.4Hz,1H),7.38-7.25(m,4H), 7.24-7.18(m,2H),7.18-7.14(m,1H),7.14-7.07(m,5H),5.91(s,1H),3.37(s,3H),3.11-3.00(m,1H),2.41-2.26(m,1H),2.12-2.04(m,1H), 1.73-1.57(m,1H),1.13(s,3H). 13 C NMR(100MHz,CDCl 3 )δ158.8,148.7, 144.4,142.7,141.3,136.5,135.0,133.8,132.7,130.2,129.8,129.0, 128.9,128.3,128.2,127.9,127.2,127.2,126.3,125.9,124.6,124.4,119.8,65.4,61.4,23.9,20.8,18.0.HRMS(ESI)m/z:[M+H] + calculated for C 32 H 28 NO Molecular Weight:442.2165,found:442.2161.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝ 99.9:0.1,0.6mL/min,254nm,97％ee)；major enantiomer tr＝6.476min,minor enantiomer tr＝5.185min.[α] D 25 ＝-274.33(c＝1,CHCl 3 ).
Example 2:
(S, E) -2-methyl-7 ',8' -diphenyl-4 ',5' -dihydro-spiro [ cyclohexane-1, 9' -cyclopenta [ E ] acenaphthylenyl ] -2-en-6-one-O-methyl oxime
To a 25mL reaction tube was added (E) -2- (1, 2-dihydronaphthalen-5-yl) -3-methylcyclohex-2-en-1-one-O-methyloxime (58 mg,0.2 mmol), diphenylacetylene (53 mg,0.3 mmol), palladium chloride (3.5 mg,0.02 mmol), boc-D-valine (8.68 mg,0.04 mmol), silver acetate (34 mg,0.2 mmol), and ethylene glycol dimethyl ether (4 mL). The reaction tube was moved to 90℃for 20 hours in an oil bath. The mixture was purified by flash column chromatography to give a yellow solid (65 mg,0.138 mmol) in 69% yield. The fluorescence emission spectrum is shown in fig. 1, and the ultraviolet absorption spectrum is shown in fig. 3.
1 H NMR(400MHz,CDCl 3 )δ7.36-7.26(m,4H),7.25-7.20(m,3H), 7.20-7.14(m,2H),7.13-7.08(m,5H),5.91(s,1H),3.41(s,3H),3.36-3.19(m,4H),3.05(m,1H),2.45-2.27(m,1H),2.20-2.07(m,1H),1.88-1.73 (m,1H),1.16(s,3H). 13 C NMR(100MHz,CDCl 3 )δ159.0,148.5,146.8,146.1, 144.8,142.2,140.6,138.9,136.6,135.5,134.0,130.1,129.9,128.3,127.8,127.8,127.2,127.0,127.0,126.1,119.5,118.2,113.7,64.4,61.4, 31.0,30.2,24.1,20.9,17.9.HRMS(ESI)m/z:[M+H] + calculated for C 34 H 30 NO Molecular Weight:468.2322,found:468.2305.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1, 0.6mL/min,254nm,97％ee)；major enantiomer tr＝10.066min,minor enantiomer tr＝9.200min.[α] D 25 ＝-274.33(c＝1,CHCl 3 ).
Example 3:
(S, E) -2-methyl-7 ',8' -diphenylspiro [ cyclohexane-1, 9' -cyclopentyl [ a ] pyrene ] -2-en-6-one-O-methyloxime
To a 25mL reaction tube was added (E) -3-methyl-2- (pyren-1-yl) cyclohex-2-en-1-one-O-methyloxime (68 mg,0.2 mmol), diphenylacetylene (71 mg,0.4 mmol), palladium trifluoroacetate (2.7 mg,0.008 mmol), boc-L-isoleucine (3.7 mg,0.016 mmol), silver acetate (67 mg,0.4 mmol), and acetic acid (2 mL). The reaction tube was moved to 80℃for 16 hours in an oil bath. The mixture was purified by flash column chromatography to give a yellow solid (92 mg,0.178 mmol) in 81% yield. The fluorescence emission spectrum is shown in fig. 1, and the ultraviolet absorption spectrum is shown in fig. 4.
1 H NMR(400MHz,CDCl 3 )δ8.13-8.03(m,3H),8.01-7.94(m,3H), 7.93-7.85(m,2H),7.41(d,J＝6.8Hz,2H),7.34-7.20(m,3H),7.20-7.10 (m,5H),6.01(s,1H),3.34(s,3H),3.22-3.09(m,1H),2.54-2.38(m,1H),2.29-2.01(m,1H),1.81-1.64(m,1H),1.17(s,3H). 13 C NMR(101MHz,CDCl 3 ) δ159.2,149.3,143.6,142.7,141.5,136.4,135.0,133.9,131.3,130.8,130.2,129.9,128.4,128.2,128.0,127.5,127.4,127.3,126.8,126.7, 126.0,125.5,125.4,125.2,124.1,124.1,117.6,65.3,61.5,23.9,21.0,18.1.HRMS(ESI)m/z:[M+H] + calculated for C 38 H 30 NO Molecular Weight: 516.2322,found:516.2335.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min,254 nm,96％ee)；major enantiomer tr＝26.586min,minor enantiomer tr＝20.934 min.[α] D 25 ＝-425.50(c＝1.8,CHCl 3 ).
Example 4:
(S, E) -2-methyl-2 ',3',5 '-triphenylspirocyclic [ cyclohexane-1, 1' -cyclopenta [ a ] naphthalene ] -2-en-6-one-O-methyloxime
To a 25mL autoclave was added (E) -3-methyl-2- (4-phenylnaphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (68 mg,0.2 mmol), diphenylacetylene (89 mg,0.5 mmol), palladium tetrafluoroacetonitrile (7.1 mg,0.016 mmol), boc-L-isoleucine (7.4 mg,0.032 mmol), silver carbonate (55 mg,0.2 mmol), acetic acid (1 mL) and acetone (3 mL). The high pressure tube was moved to 70℃for 20 hours in an oil bath and the mixture was purified by flash column chromatography to give a yellow solid (90 mg,0.174 mmol) in 87% yield. The fluorescence emission spectrum is shown in fig. 1, and the ultraviolet absorption spectrum is shown in fig. 5.
1 H NMR(400MHz,CDCl 3 )δ7.98(d,J＝8.4Hz,1H),7.79(d,J＝8.0 Hz,1H),7.58(d,J＝7.2Hz,2H),7.55-7.37(m,8H),7.35-7.21(m,8H), 6.07(s,1H),3.56(s,3H),3.29-3.18(m,1H),2.61-2.39(m,1H),2.28-2.14(m,1H),1.92-1.75(m,1H),1.34(s,3H). 13 C NMR(100MHz,CDCl 3 )δ159.1, 149.0,143.8,142.1,141.6,141.3,140.4,136.5,134.9,133.9,130.9, 130.5,130.3,129.9,129.8,129.1,128.3,128.2,127.9,127.3,127.2,127.2,127.2,126.4,125.7,124.6,121.0,65.5,61.5,23.9,20.8, 18.1.HRMS(ESI)m/z:[M+H] + calculated for C 38 H 30 NO Molecular Weight: 516.2322,found:516.2335.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min,254 nm,93％ee)；major enantiomer tr＝13.877min,minor enantiomer tr＝10.064 min.[α] D 25 ＝-425.50(c＝1.8,CHCl 3 ).
Example 5:
(S, E) -2,5 '-dimethyl-2', 3 '-diphenylspiro [ cyclohexane-1, 1' -cyclopentane [ a ] naphthalene ] -2-en-6-one-O-methyl oxime
To a 25mL autoclave was added (E) -3-methyl-2- (4-methylnaphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (56 mg,0.2 mmol), diphenylacetylene (107 mg,0.6 mmol), palladium acetate (1.8 mg,0.008 mmol), N-Boc-L-tert-leucine (3.4 mg,0.016 mmol), p-benzoquinone (22 mg,0.2 mmol), and acetone (3 mL). The high pressure tube was moved to 70℃for 10 hours in an oil bath. The mixture was purified by flash column chromatography to give a yellow solid (57 mg,0.124 mmol) in 62% yield. The fluorescence emission spectrum is shown in FIG. 1, and the ultraviolet absorption spectrum is shown in FIG. 6.
1 H NMR(400MHz,CDCl 3 )δ7.99-7.92(m,1H),7.64-7.52(m,1H), 7.40-7.33(m,2H),7.31-7.15(m,6H),7.14-7.04(m,5H),5.90(s,1H),3.38(s,3H),3.10-2.98(m,1H),2.64(s,3H),2.41-2.24(m,1H),2.18-2.01 (m,1H),1.77-1.57(m,1H),1.13(s,3H). 13 C NMR(100MHz,CDCl 3 )δ159.1, 148.6,142.6,142.3,141.4,136.5,135.1,134.3,134.0,131.8,130.3, 129.8,128.9,128.3,127.9,127.2,127.1,126.1,125.5,125.2,124.9,124.4,120.8,65.4,61.4,23.9,20.8,20.2,18.0.HRMS(ESI)m/z: [M+H] + calculated for C 33 H 30 NO Molecular Weight:456.2322,found:456.2329.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes: isopropanol＝99.9:0.1,0.6mL/min,254nm,98％ee)；major enantiomer tr ＝8.693min,minor enantiomer tr＝7.620min.[α] D 25 ＝-260.64(c＝1.0, CHCl 3 ).
Example 6:
(S, E) -2-phenyl-2 ',3' -diphenylspiro [ cyclohexane-1, 1' -cyclopentane [ a ] naphthalene ] -2-en-6-one-O-methyloxime
To a 25mL reaction tube was added (E) -3-methyl-2- (4-methylnaphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (65 mg,0.2 mmol), diphenylacetylene (39 mg,0.22 mmol), palladium trifluoroacetate (1.3 mg,0.04 mmol), N-Boc-L-tert-leucine (1.7 mg,0.008 mmol), p-benzoquinone (43 mg,0.4 mmol), and acetic acid (2 mL). The high pressure tube was moved to 60℃for 24 hours in an oil bath. The mixture was purified by flash column chromatography to give a yellow solid (79 mg,0.156 mmol) in 78% yield.
1 H NMR(400MHz,CDCl 3 )δ7.72(dd,J＝8.4,2.8Hz,H),7.59(d,J ＝8.4Hz,1H),7.38(t,J＝7.6Hz,1H),7.33-.12(m,12H),6.90-6.70(m, 5H),6.21(s,1H),3.41(s,3H),3.24-3.11(m,1H),2.63-2.50(m,1H),2.35-2.23(m,1H),2.09-2.00(m,1H). 13 C NMR(100MHz,CDCl 3 )δ158.7, 148.6,144.6,142.9,141.8,140.4,139.5,136.5,135.2,132.6,130.6, 130.6,129.6,129.2,129.0,128.4,128.1,128.0,127.3,127.1,127.0, 125.7,124.7,124.4,119.7,64.4,61.5,24.1,20.5.HRMS(ESI)m/z:[M+H + calculated for C 37 H 30 NO Molecular Weight:504.2322,found:504.2301. Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min,254nm,96％ee)；major enantiomer tr ＝16.694min,minor enantiomer tr＝9.696min.[α] D 25 ＝-230.15(c＝2,CHCl 3 ).
Example 7:
(S, E) -2-p-methylphenyl-2 ',3' -diphenylspiro [ cyclohexane-1, 1' -cyclopentane [ a ] naphthalene ] -2-en-6-one-O-methyl oxime
To a 25mL reaction tube was added (E) -3-methyl-2- (4-methylnaphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (68 mg,0.2 mmol), diphenylacetylene (53 mg,0.3 mmol), palladium chloride (2.1 mg,0.012 mmol), boc-L-phenylalanine (6.4 mg,0.024 mmol), silver acetate (100 mg,0.6 mmol), and ethylene glycol dimethyl ether (3 mL). The high pressure tube was moved to 50℃for 10 hours in an oil bath. The mixture was purified by flash column chromatography to give a yellow solid (58 mg,0.112 mmol) in 56% yield.
1 H NMR(400MHz,CDCl 3 )δ7.67(dd,J＝20.0,8.4Hz,2H),7.53(d, J＝8.4Hz,1H),7.38-7.05(m,13H),6.68(d,J＝8.0Hz,2H),6.53(d, J＝8.0Hz,2H),6.16(t,J＝4.8Hz,1H),3.34(s,3H),3.20-3.05(m,1H),2.59-2.41(m,1H),2.30-2.15(m,1H),2.02-1.94(m,1H),1.92(s, 3H). 13 C NMR(100MHz,CDCl 3 )δ158.9,148.8,144.7,142.9,141.7,139.4, 137.6,136.6,136.5,135.3,132.6,130.6,130.3,129.7,129.3,128.9,128.4,128.1,127.9,127.2,127.2,127.1,125.7,124.7,124.4,119.7,64.6, 61.5,24.2,21.0,20.5.HRMS(ESI)m/z:[M+H] + calculated for C 38 H 32 NO Molecular Weight:518.2478,found:518.2469.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1, 0.6mL/min,254nm,85％ee)；major enantiomer tr＝12.174min,minor enantiomer tr＝7.980min.[α] D 25 ＝-176.31(c＝1.1,CHCl 3 ).
Example 8:
(S, E) -2-ethyl-2 ',3' -diphenylspiro [ cyclohexane-1, 1' -cyclopentane [ a ] naphthalene ] -2-en-6-one-O-methyloxime
To a 25mL reaction tube was added (E) -3-methyl-2- (4-methylnaphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (56 mg,0.2 mmol), diphenylacetylene (71 mg,0.3 mmol), palladium trifluoroacetate (6.6 mg,0.02 mmol), boc-L-phenylalanine (10.6 mg,0.04 mmol), silver oxide (93 mg,0.6 mmol), and methylene chloride (4 mL). The high pressure tube was moved to 50 ℃ oil bath for 24 hours. The mixture was purified by flash column chromatography to give a yellow solid (45 mg,0.098 mmol) in 49% yield.
1 H NMR(400MHz,CDCl 3 )δ7.94-7.89(m,1H),7.85(d,J＝8.4Hz,1H), 7.71(d,J＝8.0Hz,1H),7.57(d,J＝8.4Hz,1H),7.50-7.36(m,4H), 7.35-7.21(m,6H),7.21-7.12(m,2H),6.07(s,1H),3.49(s,3H),3.25-3.08(m,1H),2.60-2.43(m,1H),2.33-2.16(m,1H),1.95-1.64(m,2H), 1.43-1.20(m,1H),0.84(t,J＝7.2Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ 159.2,149.4,144.8,142.8,141.4,139.0,136.5,135.0,132.7,130.4, 129.8,129.1,129.0,128.3,128.1,127.8,127.2,127.1,125.9,124.6,124.5,123.4,119.8,65.7,61.4,23.8,22.4,20.8,12.1.HRMS(ESI)m/z: [M+H] + calculated for C 33 H 30 NO Molecular Weight:456.2322,found:456.2319. Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min,254nm,96％ee)；major enantiomer tr ＝4.639min,minor enantiomer tr＝4.327min.[α] D 25 ＝-281.30(c＝0.9, CHCl 3 ).
Example 9:
(S, E) -2-methyl-2 ',3' -bis (4- (trifluoromethyl) phenyl) spiro [ cyclohexane-1, 1' -cyclopenta [ a ] naphthalene ] -2-en-6-one-O-methyl oxime
To a 25mL reaction tube was added (E) -3-methyl-2- (naphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (53 mg,0.2 mmol), 1, 2-bis (4- (trifluoromethyl) phenyl) acetylene (157 mg,0.5 mmol), palladium acetate (2.7 mg,0.012 mmol), N-acetyl-L-alanine (3.1 mg,0.024 mmol), silver acetate (34 mg,0.2 mmol), and further dichloromethane (2 mL), diethyl ether (2 mL). The high pressure tube was moved to 40 ℃ oil bath for 28 hours. The mixture was purified by flash column chromatography to give a yellow solid (83 mg,0.144 mmol) in 72% yield.
1 H NMR(400MHz,CDCl 3 )δ7.95-7.91(m,1H),7.86(d,J＝8.4Hz,1H), 7.73-7.66(m,1H),7.60(d,J＝8.2Hz,2H),7.53-7.43(m,7H),7.31-7.26(m,2H),6.06(s,1H),3.47(s,3H),3.21-3.07(m,1H),2.54-2.40(m,1H), 2.29-2.12(m,1H),1.84-1.71(m,1H),1.24(s,3H). 13 C NMR(100MHz,CDCl 3 ) δ157.9,148.2,144.9,141.6,141.5,139.8,138.3,133.1,130.4(q,J CF ＝32.5Hz),129.5(q,J CF ＝38.7Hz),129.2,128.8,128.6,127.0,126.3, 125.6(q,J CF ＝278.9Hz),125.6,125.1(q,J CF ＝3.6Hz),124.8(q,J CF ＝ 3.7Hz),124.8(q,J CF ＝281.6Hz),122.9,119.4,65.5,61.5,23.6,20.7, 18.0.HRMS(ESI)m/z:[M+H] + calculated for C 34 H 25 F 6 NO Molecular Weight: 578.1913,found:578.1926.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min,254 nm,97％ee)；major enantiomer tr＝9.454min,minor enantiomer tr＝7.382 min.[α] D 25 ＝-206.42(c＝1.6,CHCl 3 ).
Example 10:
(S, E) -2',3' -bis (4-methoxyphenyl) -2-methyl-spiro [ cyclohexane-1, 1' -cyclopenta [ a ] naphthalene ] -2-en-6-one-O-methyl oxime
To a 25mL reaction tube was added (E) -3-methyl-2- (naphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (53 mg,0.2 mmol), 1, 2-bis (4-methoxy) acetylene (143 mg,0.6 mmol), palladium trifluoroacetate (5.3 mg,0.016 mmol), N-acetyl-L-alanine (4.2 mg,0.032 mmol), silver oxide (46 mg,0.2 mmol), and diethyl ether (2 mL). The high pressure tube was moved to 40℃for 40 hours in an oil bath. The mixture was purified by flash column chromatography to give a yellow solid (53 mg,0.106 mmol) in 53% yield.
1 H NMR(400MHz,CDCl 3 )δ7.92-7.87(m,1H),7.82(d,J＝8.4Hz,1H), 7.67(dd,J＝8.0,2.0Hz,1H),7.54(d,J＝8.4Hz,1H),7.48-7.36(m, 3H),7.33-7.24(m,3H),7.14-7.06(m,2H),6.91-6.73(m,5H),5.99(s,1H),3.80(s,3H),3.78(s,3H),3.46(s,3H),3.22-3.09(m,1H),2.55-2.36 (m,1H),2.28-2.14(m,1H),1.89-1.73(m,1H),1.20(s,3H). 13 C NMR(100 MHz,CDCl 3 )δ159.2,158.7,147.8,144.3,143.1,140.5,134.1,132.6, 131.3,131.0,129.0,128.9,128.9,128.1,127.5,126.1,125.8,124.5,124.3,119.8,113.8,113.4,65.2,61.4,55.3,55.2,23.9,20.8,17.9.HRMS (ESI)m/z:[M+H] + calculated for C 34 H 32 NO 3 Molecular Weight:502.2377,found: 502.2367.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min,254nm,96％ee)；major enantiomer tr＝18.932min,minor enantiomer tr＝17.162min.[α] D 25 ＝ -218.25(c＝1,CHCl 3 ).
Example 11:
(S, E) -2-methyl-2 ',3' -bis (naphthalen-2-yl) spiro [ cyclohexane-1, 1' -cyclopentane [ a ] naphthalene ] -2-en-6-one-O-methyl oxime
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To a 25mL reaction tube was added (E) -3-methyl-2- (naphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (53 mg,0.2 mmol), 1, 2-bis (naphthalen-2-yl) ethylene (61 mg,0.22 mmol), palladium tetrafluorocarbonitrile (3.6 mg,0.008 mmol), N-benzyloxycarbonyl-L-valine (4.0 mg,0.016 mmol), silver carbonate (110 mg,0.4 mmol) and dichloromethane (2 mL). The high pressure tube was moved to 90℃for 28 hours in an oil bath. The mixture was purified by flash column chromatography to give a yellow solid (99 mg,0.182 mmol) in 91% yield.
1 H NMR(400MHz,CDCl 3 ) 1 H NMR(400MHz,CDCl 3 )δ7.88(s,1H),7.82 (d,J＝7.6Hz,1H),7.75(d,J＝8.4Hz,1H),7.70-7.48(m,9H),7.40-7.26 (m,7H),7.20(dd,J＝8.4,1.6Hz,1H),5.96(s,1H),3.39(s,3H), 3.11-2.98(m,1H),2.44-2.28(m,1H),2.12-2.00(m,1H),1.79-1.65(m, 1H),1.26(s,3H). 13 C NMR(100MHz,CDCl 3 )δ158.9,148.8,144.7,142.9, 141.9,134.1,134.0,133.5,133.1,132.9,132.7,132.7,132.5,129.1,128.9,128.9,128.7,128.7,128.3,128.3,128.1,128.1,127.9,127.8, 127.7,127.4,126.5,126.1,126.0,125.9,124.7,124.4,119.9,65.6,61.4, 23.9,20.8,18.2.HRMS(ESI)m/z:[M+H] + calculated for C 40 H 32 NO Molecular Weight:542.2478,found:542.2484.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min, 254nm,96％ee)；major enantiomer tr＝16.098min,minor enantiomer tr ＝12.316min.[α] D 25 ＝-175.97(c＝1,CHCl 3 ).
Example 12:
(S, E) -2',3' -bis (4-fluorophenyl) -2-methyl-spiro [ cyclohexane-1, 1' -cyclopenta [ a ] naphthalene ] -2-en-6-one-O-methyl oxime
To a 25mL reaction tube was added (E) -3-methyl-2- (naphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (53 mg,0.2 mmol), 1, 2-bis (4-fluorophenyl) acetylene (64 mg,0.3 mmol), palladium tetrafluorocarbonitrile (8.9 mg,0.02 mmol), N-benzyloxycarbonyl-L-valine (10 mg,0.04 mmol), p-benzoquinone (43 mg,0.4 mmol), and tetrahydrofuran (2 mL). The high pressure tube was moved to 80℃for 40 hours in an oil bath. The mixture was purified by flash column chromatography to give a yellow solid (80 mg,0.168 mmol) at 84% yield.
1 H NMR(400MHz,CDCl 3 )δ7.87-7.82(m,1H),7.77(d,J＝8.4Hz,1H), 7.62(d,J＝8.0Hz,1H),7.45-7.33(m,3H),7.27-7.20(m,2H),7.11-7.03 (m,2H),7.01-6.82(m,4H),5.96(s,1H),3.40(s,3H),3.16-3.06(m,1H),2.45-2.32(m,1H),2.18-2.06(m,1H),1.86-1.64(m,1H),1.15(s,3H). 13 C NMR(100MHz,CDCl 3 )δ162.2(d,J 1 ＝245.0Hz),162.1(d,J 1 ＝245.0 Hz),158.5,147.7,144.5,142.3,140.8,133.5,132.8,132.2(d,J 4 ＝3.4 Hz),131.8(d,J 3 ＝7.8Hz),131.3(d,J 3 ＝7.9Hz),130.7(d,J 4 ＝3.4Hz), 129.1,128.8,128.3,126.6,126.1,124.8,124.2,119.5,115.4(d,J 2 ＝ 21.2Hz),115.1(d,J 2 ＝21.1Hz),65.3,61.4,23.8,20.7,17.9.HRMS(ESI) m/z:[M+H] + calculated for C 32 H 26 F 2 NO Molecular Weight:478.1977,found: 478.1968.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min,254nm,95％ee)；major enantiomer tr＝12.761min,minor enantiomer tr＝11.676min.[α] D 25 ＝ -75.60(c＝0.5,CHCl 3 ).
Example 13:
(S, E) -2',3' -bis (4-chlorophenyl) -2-methyl-spiro [ cyclohexane-1, 1' -cyclopentyl [ a ] naphthalene ] -2-en-6-one-O-methyl oxime
To a 25mL reaction tube was added (E) -3-methyl-2- (naphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (53 mg,0.2 mmol), 1, 2-bis (4-chlorophenyl) acetylene (99 mg,0.4 mmol), palladium chloride (0.7 mg,0.04 mmol), N-benzyloxycarbonyl-L-phenylalanine (2.4 mg,0.008 mmol), silver carbonate (165 mg,0.6 mmol), and methanol (2 mL). The high pressure tube was moved to 70℃for 36 hours in an oil bath. The mixture was purified by flash column chromatography to give a yellow solid (82 mg,0.160 mmol) in 80% yield.
1 H NMR(400MHz,CDCl 3 )δ7.90-7.85(m,1H),7.80(d,J＝8.4Hz,1H), 7.65(d,J＝8.0Hz,1H),7.49-7.35(m,3H),7.31-7.15(m,6H),7.07(d, J＝8.4Hz,2H),6.00(s,1H),3.42(s,3H),3.22-3.01(m,1H),2.53-2.36 (m,1H),2.34-2.07(m,1H),1.88-1.64(m,1H),1.17(s,3H). 13 C NMR(100 MHz,CDCl 3 )δ158.3,147.8,144.6,142.0,140.9,134.6,133.4,133.4, 133.3,133.1,132.8,131.4,131.0,129.1,128.8,128.8,128.4,128.4,126.7,126.1,124.9,124.2,119.5,65.3,61.4,23.7,20.7,17.9.HRMS(ESI) m/z:[M+H] + calculated for C 32 H 26 C l2 NO Molecular Weight:510.1386,found: 510.1399.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min,254nm,95％ee)；major enantiomer tr＝5.681min,minor enantiomer tr＝6.474min.[α] D 25 ＝-207.75 (c＝1.0,CHCl 3 ).
Example 14:
(S, E) -2',3' -bis (4-bromophenyl) -2-methyl-spiro [ cyclohexane-1, 1' -cyclopenta [ a ] naphthalene ] -2-en-6-one-O-methyl oxime
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To a 25mL reaction tube was added (E) -3-methyl-2- (naphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (53 mg,0.2 mmol), 1, 2-bis (4-bromophenyl) acetylene (168 mg,0.5 mmol), palladium trifluoroacetate (4.0 mg,0.012 mmol), N-benzyloxycarbonyl-L-phenylalanine (7.2 mg,0.024 mmol), p-benzoquinone (22 mg,0.2 mmol), and tetrahydrofuran (3 mL). The high pressure tube was moved to 60℃for 48 hours in an oil bath. The mixture was purified by flash column chromatography to give a yellow solid (95 mg,0.158 mmol) at 79% yield.
1 H NMR(400MHz,CDCl 3 )δ7.95-7.89(m,1H),7.83(d,J＝8.4Hz,1H), 7.68(d,J＝7.6Hz,1H),7.50-7.34(m,7H),7.21(d,J＝8.4Hz,2H), 7.03(d,J＝8.4Hz,2H),6.03(s,1H),3.46(s,3H),3.25-3.11(m,1H),2.58-2.35(m,1H),2.31-2.17(m,1H),1.96-1.74(m,1H),1.20(s,3H). 13 C NMR(100MHz,CDCl 3 )δ158.2,147.8,144.6,141.9,140.9,135.1,133.6, 133.3,132.8,131.7,131.7,131.4,131.3,129.1,128.8,128.4,126.7,126.2,124.9,124.2,121.7,121.6,119.5,65.3,61.5,23.7,20.7,17.9. HRMS(ESI)m/z:[M+H] + calculated for C 32 H 26 Br 2 NO Molecular Weight:598.0376, found:598.0395.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min,254nm,93％ ee)；major enantiomer tr＝13.945min,minor enantiomer tr＝12.043min. [α] D 25 ＝-173.60(c＝1.0,CHCl 3 ).
Example 15:
(S, E) -2',3' -bis (3-bromophenyl) -2-methyl-spiro [ cyclohexane-1, 1' -cyclopenta [ a ] naphthalene ] -2-en-6-one-O-methyl oxime
To a 25mL reaction tube was added (E) -3-methyl-2- (naphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (53 mg,0.2 mmol), 1, 2-bis (3-bromophenyl) acetylene (168 mg,0.5 mmol), palladium acetate (2.7 mg,0.012 mmol), N-acetyl-L-leucine (2.8 mg,0.024 mmol), silver carbonate (55 mg,0.2 mmol), and methanol (2 mL). The high pressure tube was moved to 50 ℃ for oil bath reaction for 36 hours. The mixture was purified by flash column chromatography to give a yellow solid (89 mg,0.148 mmol) in 74% yield.
1 H NMR(400MHz,CDCl 3 )δ7.95-7.90(m,1H),7.85(d,J＝8.4Hz,1H), 7.72-7.67(m,1H),7.57(t,J＝1.6Hz,1H),7.52-7.41(m,4H),7.41-7.36 (m,2H),7.26-7.16(m,2H),7.14-7.05(m,2H),6.06(s,1H),3.48(s,3H),3.23-3.12(m,0H),2.55-2.38(m,1H),2.29-2.15(m,1H),1.97-1.77(m, 1H),1.21(s,3H). 13 C NMR(100MHz,CDCl 3 )δ13C NMR(101MHz,CDCl3)δ158.0,147.6,144.7,141.7,141.0,138.1,136.7,133.2,132.9,132.6, 132.4,130.7,130.5,130.1,129.6,129.1,129.0,128.8,128.5,126.9,126.2,125.0,124.2,122.5,122.0,119.5,65.3,61.5,23.7,20.7,18.0. HRMS(ESI)m/z:[M+H] + calculated for C 32 H 26 Br 2 NO Molecular Weight:598.0376, found:598.0389.Enantiomeric excess was determined by HPLC with aChiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min,254nm,97％ ee)；major enantiomer tr＝16.507min,minor enantiomer tr＝14.324min. [α] D 25 ＝-146.31(c＝1.0,CHCl 3 ).
Example 16:
(S, E) -2',3' -bis (2-fluorophenyl) -2-methyl spiro [ cyclohexane-1, 1' -cyclopenta [ a ] naphthalene ] -2-en-6-one-O-methyl oxime
To a 25mL reaction tube was added (E) -3-methyl-2- (naphthalen-1-yl) cyclohex-2-en-1-one-O-methyloxime (53 mg,0.2 mmol), 1, 2-bis (2-fluorophenyl) acetylene (128 mg,0.6 mmol), palladium chloride (2.8 mg,0.016 mmol), N-acetyl-L-leucine (5.5 mg,0.032 mmol), p-benzoquinone (65 mg,0.6 mmol), and methanol (3 mL). The high pressure tube was moved to 40 ℃ oil bath for 48 hours. The mixture was purified by flash column chromatography to give a yellow solid (87 mg,0.182 mmol) in 91% yield.
1 H NMR(400MHz,CDCl 3 )δ7.84-7.77(m,1H),7.73(d,J＝8.4Hz,1H), 7.56(d,J＝7.9Hz,1H),7.39-7.30(m,2H),7.25(d,J＝8.3Hz,1H), 7.20-7.09(m,4H),7.03-6.87(m,3H),6.86-6.79(m,1H),5.87(s,1H),3.40(s,3H),3.16-2.97(m,1H),2.36-2.22(m,1H),2.03-1.87(m,1H), 1.81-1.62(m,1H),1.13(s,3H). 13 C NMR(100MHz,CDCl 3 )δ144.3(d,J 1 ＝237.2Hz),132.7,131.8,131.5,129.6,(d,J 3 ＝7.8Hz),129.0,128.8, 128.3,126.4,126.0,124.8,124.4,124.0(d,J 4 ＝3.5Hz),123.7,123.6, 123.5(d,J 4 ＝3.3Hz),119.7,115.5(d,J 2 ＝22.6Hz),65.7,61.5,23.7, 20.9,17.9.HRMS(ESI)m/z:[M+Na] + calculated for C 32 H 25 F 2 NNaO Molecular Weight:500.1796,found:500.1783.Enantiomeric excess was determined by HPLC with a Chiralpak MD(n-hexanes:isopropanol＝99.9:0.1,0.6mL/min, 254nm,97％ee)；major enantiomer tr＝21.901min,minor enantiomer tr ＝18.057min.[α] D 25 ＝-202.88(c＝1.7,CHCl 3 ).
The compounds a-e prepared in examples 1-5 were dissolved in methylene chloride (10 -5 M), the solution was subjected to uv-vis absorption and fluorescence spectrum measurements, giving the data of table 1. The fluorescence emission spectrum is shown in FIG. 1, and the ultraviolet absorption spectrum is shown in FIGS. 2-6.
Table 1 optical properties of the compounds obtained by the preparation of examples 1 to 5
Examples Compounds of formula (I) Maximum absorption wavelength/nm Maximum emission wavelength/nm Fluorescence quantum yield
1 a 328 424 0.50
2 b 338 436 0.38
3 c 350 416 0.19
4 d 331 428 0.44
5 e 333 428 0.48

Claims (6)

1. An indene chiral spiro fluorescent compound is characterized in that the structural formula of the compound is any one of the compounds shown in the following formulas a to e:
2. the method for synthesizing indene chiral spiro-fluorescent compound according to claim 1, wherein 2-arylcyclohex-2-en-1-one oxime ether of the general formula (2) and diaryl acetylene of the general formula (3) are used as reactants, a complex formed by palladium salt and chiral ligand is used as a catalyst precursor, the reaction is carried out in the presence of an oxidant in a reaction medium and air at 40-90 ℃ for 10-48h, and the product is separated after the reaction is finished, wherein the synthetic route is as follows:
the chiral ligand is any one of Boc-D-valine, boc-L-isoleucic acid, boc-L-phenylalanine, N-Boc-L-tertiary leucine, N-acetyl-L-alanine, N-benzyloxycarbonyl-L-valine, N-benzyloxycarbonyl-L-phenylalanine and N-acetyl-L-leucine; the palladium salt is one or more of palladium chloride, palladium acetate, palladium trifluoroacetate and tetraacetonitrile tetrafluoroboric acid palladium; the oxidant is any one or more of silver acetate, silver oxide, silver carbonate and p-benzoquinone.
3. The method according to claim 2, wherein the reaction medium is a mixture of any one or more of methanol, tertaol, tetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane, acetic acid, and acetone.
4. The method according to claim 2, wherein the amount of diaryl acetylene in the reaction liquid is 110 to 300mol% of 2-aryl cyclohex-2-en-1-one oxime ether.
5. The method according to claim 4, wherein the palladium salt is used in an amount of 1 to 10mol% of 2-arylcyclohex-2-en-1-one oxime ether; the dosage of the ligand is 2-20mol% of 2-aryl cyclohex-2-ene-1-ketoxime ether; the usage amount of the oxidant is 100-300 mol% of 2-aryl cyclohex-2-en-1-one oxime ether.
6. The use of the indene chiral spiro fluorescent compound according to claim 1 as a chiral organic luminescent material.
CN202210714297.2A 2022-06-22 2022-06-22 Indene chiral spiro fluorescent compound, and preparation method and application thereof Active CN114907231B (en)

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