CN113773227B - Method for preparing epsilon-, zeta-, eta-cyano carboxylic acid from carbon dioxide - Google Patents

Method for preparing epsilon-, zeta-, eta-cyano carboxylic acid from carbon dioxide Download PDF

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CN113773227B
CN113773227B CN202111000883.2A CN202111000883A CN113773227B CN 113773227 B CN113773227 B CN 113773227B CN 202111000883 A CN202111000883 A CN 202111000883A CN 113773227 B CN113773227 B CN 113773227B
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孙松
柏君雪
周聪
李渺
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/34—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention relates to the fields of medicine, organic chemical industry and fine chemical industry, in particular to a method for preparing epsilon-, zeta-, eta-cyano carboxylic acid from carbon dioxide. The method comprises the steps of taking olefin and cyclic ketoxime as raw materials, taking iridium, 4CZIPN or ruthenium as catalysts, taking dimethyl sulfoxide as a solvent in the presence of a reducing agent, reacting for 12-24 hours at room temperature with a 2x3W blue LED, adding methyl iodide, and carrying out synthetic reaction in an oil bath kettle at 50 ℃ for 1 hour to obtain the product. The product after the reaction is simply post-treated to obtain a series of epsilon-, zeta-, eta-cyano carboxylic acid compounds with high yield. Stilbene with various substituents and cyclic ketoxime with various substituents can be used as reaction substrates to obtain corresponding epsilon-, zeta-, eta-cyano carboxylic acid compounds.

Description

Method for preparing epsilon-, zeta-, eta-cyano carboxylic acid from carbon dioxide
Technical Field
The invention relates to the fields of medicine, organic chemical industry and fine chemical industry, in particular to a simple and efficient method for synthesizing epsilon-, zeta-, eta-cyano carboxylic acid compounds by taking carbon dioxide, olefin and cyclic ketoxime as raw materials, DIPEA or triethylamine as a reducing agent and DMSO as a solvent under the catalysis of iridium, 4CzIPN or ruthenium.
Background
Cyanocarboxylic acids are an important class of bioactive compounds and are also important intermediates in the construction of pharmaceutical molecules such as vitamin B6, caffeine, folic acid and the like (see (a) Oliver, l.; jens-Uwe, r.; hilke-Marie, l.; paul, h.; constanze, m.preparation cyano carboxylic acid esters, EP 2455365A1,20120523, (B) Michael Paul, B.; john Wing, w.biocatalytic preparation of 1-cyancycloxaacetic acid, WO 2004111256A1,20041223). In addition, cyano groups in the structure of the aliphatic dicarboxylic acid compound can be hydrolyzed into carboxyl groups, and the aliphatic dicarboxylic acid compound has wide application in high-molecular polymerization reaction, is an important monomer for synthesizing polyamide and polyester, so that the effective synthesis of the aliphatic dicarboxylic acid compound has high application value (see, ren, W.; chu, J.; sun, F.; shi, Y.org. Lett.2019,21,5967-5970, (b) Yang, J.; liu, J.; ge, Y.; huang, W.; neumann, H.; jacksell, R.; beller, M.Angew.chem. Int. Ed.2020,59, 20394-20398.). The classical synthesis method of the compound is prepared by nucleophilic substitution reaction of halogenated carboxylic acid and sodium cyanide or hydrocyanic acid, however, the method needs extremely toxic sodium cyanide or hydrocyanic acid, and brings great trouble to actual operation; in addition, the single cyano hydrolysis of dinitriles is an important class of process for the preparation of cyanocarboxylic acids, however, the two cyano groups in the compounds have similar reactivity, and it is a challenging task to control the reaction conditions to ensure that only one cyano group is hydrolyzed (see: zhu, d.; mukherJee, c.; biehl, e.r.; hua, l. Adv. Synth. Catalyst. 2007,349, 1667-1670.).
Recently, it was reported in the professor da that a series of cyanocarboxylic acids could be obtained by ring-opening carboxylation of cyclic ketoxime esters with carbon dioxide, however the reaction was limited to 2-aryl substituted cyclic ketoxime esters, the substrate application range was narrow and the substrate synthesis difficulty was great (see: jiang, y.—x.; chen, l.; ran, c.+ -. K.; song, l.; zhang, w.; liao, l.+ -. L.; yu, d.—g.chemsuschem 2020,13,6312-6317.). Further development realizes the rapid construction of cyano carboxylic acid compounds with different carbon chain lengths by a simple and easily obtained raw material and a method with mild reaction conditions, and has higher research value.
Disclosure of Invention
In view of the shortcomings in the background art, the invention takes cheap and easily available carbon dioxide, olefin and cyclic ketoxime (2-position, 3-position substituted cyclic ketoxime, cyclopentanone oxime, cyclohexanone oxime and the like) as starting materials, and synthesizes a series of epsilon-, zeta-, eta-cyano carboxylic acids through continuous free radical addition/single electron reduction/carboxylation reaction under the catalysis of iridium, 4CZIPN or ruthenium under the promotion of visible light. The method has the advantages of wide sources of raw materials, simple and convenient operation method, easy separation and purification and higher yield.
The synthesis method of the epsilon-, zeta-, eta-cyano carboxylic acid compound comprises the following steps: olefin and cycloketoxime are used as raw materials, iridium, 4CZIPN or ruthenium is used as a photocatalyst, dimethyl sulfoxide is used as a solvent in the presence of a reducing agent, and carbon dioxide gas is filled after all the raw materials participating in the reaction are added, so that a series of cyano carboxylic acid compounds are obtained.
The specific process of the reaction is as follows:
r' R on the olefin is phenyl, methyl, naphthyl, thienyl or hydrogen; when R' and R are phenyl, the substituent groups are fluorine, chlorine, bromine, methoxy, ester groups and p-trifluoromethyl; r is R 1 Is methyl or hydrogen.
The structural formula of the raw material olefin is as follows:r' R on the olefin is phenyl, methyl, naphthyl, thienyl or hydrogen; when R' and R are phenyl, the substituent groups are fluorine, chlorine, bromine, methoxy, ester groups and p-trifluoromethyl; r is R 1 Is methyl or hydrogen.
The cyclic ketoxime is selected from four-membered ring, six-membered ring, heterocycle and various substituent products carried by the ring ketoxime.
The structural formula of the raw material cyclic ketoxime is as follows:r on cyclic ketoxime 3 、R 4 、R 5 One selected from aryl, methyl, cyano, benzyl and ester; x is C, O, N; r is R 2 ＝p-CF 3 C 6 H 4 CO，n＝1，2，3。
The specific reaction conditions of the invention are as follows: 2x3W blue LED, and then adding into an oil bath pot with methyl iodide at 50 ℃ for further reaction for 1 hour.
The photocatalyst used in the reaction is bis [2- (2, 4-difluorophenyl) -5-trifluoromethylpyridine ] [2-2 '-bis (4-tert-butylpyridine) ] iridium bis (hexafluorophosphate), tris (2, 2' -bipyridine) ruthenium bis (hexafluorophosphate), and 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile, wherein the dosage of the catalyst is 2mol% of the mole number of olefin;
the molar ratio of olefin to cyclic ketoxime used was 1:1.5, the pressure of the carbon dioxide is 0.1MPa;
the reducing agent is N, N-Diisopropylethylamine (DIPEA), or triethylamine (Et) 3 N); the molar ratio of the catalyst to the olefin is 3.0:1.
the molar ratio of methyl iodide to olefin is 4:1.
the reaction post-treatment is simple and convenient, and the pure epsilon-, zeta-, eta-cyano carboxylic acid compound can be obtained by using a simple column chromatography separation method and using a mixed solvent of petroleum ether and ethyl acetate as an eluent.
The starting olefins and cyclic ketoximes employed in the present invention are synthesized in accordance with literature (Cheng, z.; jin, w.; liu, c.b.) 2 pin 2 -catalyzed oxidative cleavage of a C＝C double bond with molecular oxygen,Org.Chem.Front.2019,6,841-845；Zhao,B.；Shi,Z.Angew.Chem.Int.Ed.2017,56,12727–12731.)。
The beneficial effects are that:
the invention synthesizes a series of epsilon-, zeta-, eta-cyano carboxylic acid compounds by using olefin and cyclic ketoxime for the first time, provides a simpler and feasible way and has important application value.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are presented in the following examples:
example 16 methyl cyano-2, 2-diphenylhexanoate
Methyl 6-cyano-2,2-diphenylhexanoate
1, 1-stilbene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 76% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.34–7.28(m,10H),3.71(s,3H),2.43–2.38(m,2H),2.27(t,J＝7.2Hz,2H),1.68-1.60(m,2H),1.26-1.19(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.5,142.4,128.7,127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8 mass spectrometry data: MS (EI) 307.2 (M) + )。
Example 26 methyl-cyano-2-phenyl-2- (p-tolyl) hexanoate
Methyl 6-cyano-2-phenyl-2-(p-tolyl)hexanoate
1-methyl-4- (1-phenylvinyl) benzene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 60% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl3)δ7.28–7.19(m,6H),7.11–7.06(m,4H),3.64(s,3H),2.35-2.32(m,2H),2.30(s,3H),2.22(t,J＝7.3Hz,2H),1.62–1.55(m,2H),1.20–1.14(m,2H). 13 c NMR (101 mhz, cdcl 3)) δ 174.64,142.61,139.38,136.53,128.66,128.63,128.56,127.88,126.79,119.53,59.78,52.35,37.33,25.78,24.56,20.89,16.87 mass spectrometry data: MS (EI) 321.2 (M) + )。
Example 3: 6-cyano-2- (4-methoxyphenyl) -2-phenylhexanoic acid methyl ester
Methyl 6-cyano-2-(4-methoxyphenyl)-2-phenylhexanoate
1-methoxy-4- (1-phenylvinyl) benzene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm)). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 68% yield. Nuclear magnetic data: 1 H NMR(400MH z,CDCl 3 )δ7.36–7.26(m,5H),7.24–7.21(m,2H),6.90–6.86(m,2H),3.84(s,3H),3.73(s,3H),2.42–2.37(m,2H),2.30(t,J＝7.3Hz,2H),1.70–1.63(m,2H),1.27–1.20(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.7,158.3,142.8,134.3,129.8,128.6,127.9,126.8,119.5,113.2,59.4,55.1,52.3,37.4,25.8,24.6,16.9 mass spectrometry data: MS (EI) 337.2 (M) + )。
Example 4: 6-cyano-2- (4-fluorophenyl) -2-phenylhexanoic acid methyl ester
Methyl 6-cyano-2-(4-fluorophenyl)-2-phenylhexanoate
1-fluoro-4- (1-phenylvinyl) benzene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in yield56%. Nuclear magnetic data: 1 H NMR(400MHz,CDCl3)δ7.33–7.26(m,3H),7.24–7.20(m,4H),6.98(t,J＝8.7Hz,2H),3.67(s,3H),2.38–2.34(m,2H),2.27(t,J＝7.2Hz,2H),1.66–1.59(m,2H),1.26–1.16(m,2H). 13 c NMR (101 mhz, cdcl 3) delta 174.3,142.3,130.4,130.4,128.5,128.1,127.0,114.9,114.6,59.6,52.5,37.4,25.7,24.5,16.9 mass spectrometry data: MS (EI) 325.2 (M) + )。
Example 5:2- (4-chlorophenyl) -6-cyano-2-phenylhexanoic acid methyl ester
Methyl 2-(4-chlorophenyl)-6-cyano-2-phenylhexanoate
1-chloro-4- (1-phenylvinyl) benzene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 59% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.34–7.27(m,5H),7.24–7.19(m,4H),3.70(s,3H),2.37(t,J＝8.1Hz,2H),2.28(t,J＝7.2Hz,2H),1.68–1.61(m,2H),1.27–1.18(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.1,142.1,141.1,132.8,130.2,128.5,128.1,128.1,127.1,119.4,59.7,52.5,37.2,25.7,24.5,16.9 mass spectrometry data: MS (EI) 341.1 (M) + )。
Example 6:2- (4-bromophenyl) -6-cyano-2-phenylhexanoic acid methyl ester
Methyl 2-(4-bromophenyl)-6-cyano-2-phenylhexanoate
1-bromo-4- (1-phenylvinyl) benzene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 83% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.44(d,J＝8.6Hz,2H),7.35–7.28(m,4H),7.23(d,J＝7.0Hz,3H),7.15(d,J＝8.6,2H),3.71(s,3H),2.37(t,J＝8.1Hz,2H),2.29(t,J＝7.2Hz,2H),1.68–1.61(m,2H),1.24–1.15(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 173.9,141.9,141.6,131.0,130.5,128.4,128.1,127.1,121.0,119.4,59.7,52.5,37.1,25.6,24.5,16.8 mass spectrometry data: MS (EI) 385.1 (M) + )。
Example 7: 6-cyano-2-phenyl-2- (4- (trifluoromethyl) phenyl) hexanoic acid methyl ester
Methyl 6-cyano-2-phenyl-2-(4-(trifluoromethyl)phenyl)hexanoate
1- (1-Phenylvinyl) -4- (trifluoromethyl) benzene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3)mmol)、Ir[(dF(CF 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 44% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.52(d,J＝8.4Hz,2H),7.34(d,J＝8.2Hz,2H),7.31–7.27(m,2H),7.26–7.22(m,1H),7.20–7.17(m,2H),3.67(s,3H),2.39–2.34(m,2H),2.24(t,J＝7.2Hz,2H),1.65–1.57(m,2H),1.19–1.12(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 173.8,141.7,129.2,128.5,128.2,127.3,124.9,124.8,119.4,60.1,52.6,37.2,25.7,24.5,16.9 mass spectrometry data: MS (EI) 375.1 (M) + )。
Example 8: 6-cyano-2-phenyl-2- (m-tolyl) hexanoic acid methyl ester
Methyl 6-cyano-2-phenyl-2-(m-tolyl)hexanoate
1-methyl-3- (1-phenylvinyl) benzene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50 ℃Stirring was carried out for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 ml×6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 59% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.33–7.18(m,6H),7.07(t,J＝10.4Hz,3H),3.70(s,3H),2.40–2.34(m,2H),2.33(s,3H),2.27(t,J＝7.3Hz,2H),1.67–1.59(m,2H),1.27–1.17(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.6,142.5,142.4,137.5,129.2,128.7,127.9,127.8,127.6,126.9,125.8,119.5,60.0,52.3,37.3,25.8,24.6,21.6,16.8 mass spectrometry data: MS (EI) 321.2 (M) + )。
Example 9:2- (2-chlorophenyl) -6-cyano-2-phenylhexanoic acid methyl ester
Methyl 2-(2-chlorophenyl)-6-cyano-2-phenylhexanoate
1-chloro-2- (1-phenylvinyl) benzene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 66% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.3–7.30(m,3H),7.26–7.22(m,5H),7.17–7.13(m,1H),3.71(s,3H),2.39–2.35(m,2H),2.28(t,J＝7.2Hz,2H),1.68–1.61(m,2H),1.23–1.14(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.1,140.2,134.1,131.0,130.9,128.9,128.3,128.1,127.3,126.1,59.2,52.5,33.1,25.6,24.2,16.9 mass spectrometry data: MS (EI) 282.1 (M) + )。
Example 10: 6-cyano-2- (2, 4-dichlorophenyl) -2-phenylhexanoic acid methyl ester
Methyl 6-cyano-2-(2,4-dichlorophenyl)-2-phenylhexanoate
2, 4-dichloro-1- (1-phenylvinyl) benzene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 67% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.44(d,J＝7.4Hz,2H),7.40(d,J＝2.2Hz,1H),7.38–7.28(m,3H),7.16(dd,J＝8.6,2.2Hz,1H),7.00(d,J＝8.6Hz,1H),3.66(s,3H),2.69–2.61(m,1H),2.54–2.46(m,1H),2.35–2.21(m,2H),1.75–1.56(m,2H),1.43–1.33(m,1H),0.96–0.86(m,1H). 13 CNMR(101MHz,CDCl 3 ) Delta 173.7,139.0,138.9,134.8,133.4,131.9,130.6,128.8,128.3,127.5,126.4,119.3,58.9,52.6,33.1,25.6,24.2,16.9 mass spectrometry data: MS (EI) 375.1 (M) + )。
Example 11: 6-cyano-2, 2-di-p-tolylcaproic acid methyl ester
Methyl 6-cyano-2,2-di-p-tolylhexanoate
4,4' - (ethylene-1, 1-diyl) bis (toluene) (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 62% yield. Nuclear magnetic data: 1 H NMR(400MH z,CDCl3)δ7.15-7.13(m,2H),7.12-7.13(d,J＝2.9Hz,6H),7.10(s,1H),3.68(s,3H),2.37(s,1H),2.34(s,6H),2.32(s,1H),2.28(s,2H),1.63(t,J＝7.6Hz,2H),1.25–1.20(m,2H). 13 c NMR (101 mhz, cdcl 3) delta 174.8,139.5,136.4,128.6,128.5,119.6,77.3,77.00,76.7,59.5,52.3,37.4,25.8,24.6,20.9,16.9 mass spectrometry data: MS (EI): 335.2 (M+).
Example 12:2, 2-bis (4-chlorophenyl) -6-cyanohexanoic acid methyl ester
Methyl 2,2-bis(4-chlorophenyl)-6-cyanohexanoate
4,4' - (ethylene-1, 1-diyl) bis (chlorobenzene) (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO(2.0 mL) was added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 33% yield. Nuclear magnetic data: 1 H NMR(400MH z,CDCl 3 )δ7.30–7.26(m,4H),7.17–7.14(m,4H),3.69(s,3H),2.34–2.26(m,4H),1.64(t,J＝7.5Hz,2H),1.25–1.17(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 173.7,140.7,133.1,130.0,128.3,119.4,59.3,52.7,37.2,25.7,24.5,16.9 mass spectrometry data: MS (EI) 375.1 (M) + )。
Example 13: 6-cyano-2- (naphthalen-2-yl) -2-phenylhexanoic acid methyl ester
Methyl 6-cyano-2-(naphthalen-2-yl)-2-phenylhexanoate
2- (1-Phenylvinyl) naphthalene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. Residual ofPurification of the material by flash chromatography on silica gel (PE/EA 5/1) gave the desired product in 82% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.71–7.68(m,3H),7.64(d,J＝8.8Hz,1H),7.36(d,J＝9.8Hz,2H),7.22–7.16(m,6H),3.60(s,3H),2.44–2.32(m,2H),2.13(t,J＝7.3Hz,2H),1.57–1.49(m,2H),1.18–1.12(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.3,142.4,139.7,132.7,132.1,128.7,128.1,128.0,127.5,127.3,127.2,127.1,126.9,126.1,126.1,119.5,60.1,52.4,37.20,25.7,24.6,16.8 mass spectrometry data: MS (EI) 357.2 (M) + )。
Example 14: 6-cyano-2-phenyl-2- (thiophen-2-yl) hexanoic acid methyl ester
Methyl 6-cyano-2-phenyl-2-(thiophen-2-yl)hexanoate
2- (1-Phenylvinyl) thiophene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 56% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.34–7.27(m,4H),7.25(d,J＝6.7Hz,2H),6.98(t,J＝4.7Hz,2H),3.75(s,3H),2.51–2.36(m,2H),2.29(t,J＝7.2Hz,2H),1.70–1.62(m,2H),1.40–1.30(m,2H). 13 C NMR(101MHz,CDCl 3 )δ173.6,145.8,142.8,128.1,127.4,127.2,127.0,126.2,125.1,1194,57.8,52.6,39.1,25.6,24.6,16.9 mass spectrometry data: MS (EI) 313.1 (M) + )。
Example 15: (R) -6-cyano-3-methyl-2, 2-diphenylhexanoic acid methyl ester
Methyl(R)-6-cyano-3-methyl-2,2-diphenylhexanoate
1-methyl-2, 2-diphenylethylene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 14% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.31–7.24(m,11H,overlapped with CDCl 3 ),3.62(s,3H),3.14–3.06(m,1H),2.34–2.29(m,2H),1.77–1.66(m,4H),0.85(d,J＝6.6Hz,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.6,127.5,126.9,126.9,119.6,65.6,52.3,35.5,29.7,24.0,17.3 mass spectrometry data: MS (EI) 321.2 (M) + )。
Example 16: 6-cyano-2-methyl-2- (naphthalen-2-yl) hexanoic acid methyl ester
Methyl 6-cyano-2-methyl-2-(naphthalen-2-yl)hexanoate
2- (1-methyl vinyl) naphthalene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2X3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 25% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.84–7.79(m,3H),7.72(d,J＝2.0Hz,1H),7.50–7.45(m,2H),7.40(dd,J＝8.8,2.0Hz,1H),3.67(s,3H),2.33–2.29(m,2H),2.17–2.00(m,2H),1.69(s,3H),1.67–1.63(m,2H),1.40–1.30(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 176.5,140.5,133.2,132.2,128.2,128.0,127.4,126.2,126.0,124.4,124.3,119.5,52.3,50.1,38.4,25.8,23.9,22.4,17.0 mass spectrometry data: MS (EI) 295.2 (M) + )。
Example 17: (S) -4- (6-cyano-1-methoxy-1-oxohex-2-yl) benzoic acid methyl ester
Methyl(S)-4-(6-cyano-1-methoxy-1-oxohexan-2-yl)benzoate
Methyl 4-vinylbenzoate (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, schlenk tube is placed in the chamberStirring is carried out for 12 hours at a temperature under the irradiation of a 2X3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 72% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.98(d,J＝8.4Hz,2H),7.34(d,J＝8.4Hz,2H),3.89(s,3H),3.65(s,3H),3.59(t,J＝7.6Hz,1H),2.30(t,J＝7.1Hz,2H),2.16–2.07(m,1H),1.82–1.76(m,1H),1.69–1.63(m,2H),1.44–1.33(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 173.4,166.7,143.6,130.0,129.3,127.8,119.3,52.2,52.1,51.2,32.4,26.5,25.0,16.9 mass spectrometry data: MS (EI) 289.1 (M) + )。
Example 18:5- (cyanomethyl) -2, 2-diphenyladipic acid dimethyl ester
Dimethyl 5-(cyanomethyl)-2,2-diphenylhexanedioate
1, 1-stilbene (0.2 mmol), 3- (((4- (trifluoromethyl) benzoyl) oxy) imino) cyclobutane-1-carboxylic acid methyl ester (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 60% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.30(dd,J＝14.2,6.6Hz,6H),7.25–7.21(m,4H),3.71(s,3H),3.69(s,3H),2.70–2.57(m,2H),2.51–2.40(m,2H),2.37–2.29(m,1H),1.59–1.40(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 172.7,142.1,142.0,128.6,128.6,128.0,127.0,59.9,52.5,52.3,41.6,34.9,27.2,19.1 mass spectrometry data: MS (EI) 365.2 (M) + )。
Example 19: 6-cyano-2, 5-triphenylhexanoic acid methyl ester
Methyl 6-cyano-2,2,5-triphenylhexanoate
1, 1-stilbene (0.2 mmol), 3-phenylcyclobutan-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 77% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.35–7.28(m,9H),7.20(d,J＝7.4Hz,4H),7.10(d,J＝7.0Hz,2H),3.67(s,3H),2.89–2.81(m,1H),2.49(d,J＝7.0Hz,2H),2.40–2.33(m,1H),2.24–2.17(m,1H),1.68–1.52(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.4,142.3,142.2,141.0,128.7,128.6,127.9,127.9,127.4,127.2,126.9,126.8,118.2,60.0,52.3,42.4,35.7,30.2,25.3 mass spectrometry data: MS (EI) 383.2 (M) + )。
Example 20: 5-benzyl-6-cyano-2, 2-diphenylhexanoic acid methyl ester
Methyl 5-benzyl-6-cyano-2,2-diphenylhexanoate
1, 1-stilbene (0.2 mmol), 3-benzylcyclobutan-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 71% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDC l 3 )δ7.28(t,J＝7.1Hz,4H),7.25–7.18(m,9H),7.06(d,J＝6.7Hz,2H),3.67(s,3H),2.73(dd,J＝13.8,5.6Hz,1H),2.52–2.39(m,3H),2.23(dd,J＝16.8,5.4Hz,1H),2.13(dd,J＝16.9,5.6Hz,1H),1.90–1.86(m,1H),1.29–1.25(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.4,142.4,142.3,138.6,128.9,128.7,128.6,128.5,127.9,127.9,126.9,126.9,126.4,118.3,60.1,52.4,39.4,37.7,35.5,29.0,20.9 mass spectrometry data: MS (EI) 397.2 (M) + )。
Example 21:5- (benzyloxy) -6-cyano-2, 2-diphenylhexanoic acid methyl ester
Methyl 5-(benzyloxy)-6-cyano-2,2-diphenylhexanoate
1, 1-diphenyl ethylene0.2 mmol), 3-benzyloxycyclobutane-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 50% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.24–7.10(m,15H),4.38(q,J＝11.6Hz,2H),3.57(s,3H),3.52–3.45(m,1H),2.36(d,J＝5.9Hz,2H),2.25–2.17(m,1H),1.39–1.23(m,2H),1.15–1.08(m,1H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.4,142.4,142.1,137.4,128.8,128.7,128.4,128.0,127.9,127.8,127.0,126.9,117.5,74.4,71.6,59.9,52.4,33.1,29.5,22.8 mass spectrometry data: MS (EI) 413.2 (M) + )。
Example 22:5- (((benzyloxy) carbonyl) amino) -6-cyano-2, 2-diphenylhexanoic acid methyl ester
Methyl 5-(((benzyloxy)carbonyl)amino)-6-cyano-2,2-diphenylhexanoate
Benzyl 1, 1-stilbene (0.2 mmol), (3- (((4- (trifluoromethyl) benzoyl) oxy) imino) cyclobutyl) carbamate (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)·PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, schlenk tubeStir at room temperature for 12 hours under 2x3W blue LED illumination. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 39% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.36–7.27(m,12H),7.24–7.18(m,3H),5.14–5.08(m,4H),3.70(s,3H),2.78–2.64(m,1H),2.56–2.44(m,2H),2.37–2.31(m,1H),1.33(d,J＝6.9Hz,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.4,155.8,142.3,142.1,136.0,128.6,128.6,128.5,128.5,128.2,128.2,128.1,128.1,128.1,128.0,127.1,127.1,117.0,66.9,59.9,52.6,48.2,43.6,34.6,29.5,25.0,23.8,19.4 mass spectrometry data: MS (EI) 456.2 (M) + )。
Example 23:5, 6-dicyano-2, 2-diphenylhexanoic acid methyl ester
Methyl 5-(((benzyloxy)carbonyl)amino)-6-cyano-2,2-diphenylhexanoate
1, 1-stilbene (0.2 mmol), 3-cyanocyclobutan-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5Purification 1) gives the desired product in 80% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.33–7.28(m,6H),7.23(d,J＝1.8Hz,1H),7.22–7.19(m,3H),3.68(s,3H),2.77–2.73(m,1H),2.59(dd,J＝6.8,4.0Hz,2H),2.49–2.42(m,1H),1.54–1.48(m,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.0,141.7,141.7,128.5,128.5,128.2,128.2,127.3,118.7,115.4,59.7,52.6,35.3,28.6,27.7,20.7 mass spectrometry data: MS (EI) 332.2 (M) + )。
Example 24: 6-cyano-5-methyl-2, 5-triphenylhexanoic acid methyl ester
Methyl 6-cyano-5-methyl-2,2,5-triphenylhexanoate
1, 1-stilbene (0.2 mmol), 3-methyl-3-phenylcyclobutan-1-one O- (4- (trifluoromethyl) benzyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 70% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.35–7.28(m,9H),7.19–7.16(m,4H),7.13(d,J＝7.4Hz,2H),3.67(s,3H),2.62–2.51(m,2H),2.30–2.22(m,1H),2.10–2.01(m,1H),1.73–1.65(m,1H),1.56(dd,J＝12.7,4.2Hz,1H),1.51(s,3H). 13 C NMR(101MHz,CDCl 3 )δ174.3,143.4,142.3,142.2,128.7,128.7,128.5,127.9,127.9,126.8,126.7,125.7,117.8,59.8,52.3,40.0,36.4,32.7,31.7,24.8. mass spectrometry data: MS (EI) 397.2 (M) + )。
Example 25:4- (cyanomethyl) -4- (4-methoxy-4-oxo-3, 3-diphenylbutyl) piperidine-1-carboxylic acid tert-butyl ester
tert-Butyl4-(cyanomethyl)-4-(4-methoxy-4-oxo-3,3-diphenylbutyl)piperidine-1-carboxylate
Stilbene (0.2 mmol), 2- (((4- (trifluoromethyl) benzoyl) oxy) imino) -7-azaspiro [3.5 ]]Nonane-7-carboxylic acid tert-butyl ester (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 76% yield. Nuclear magnetic data: 1 H NM R(400MHz,CDCl 3 )δ7.29(d,J＝8.8Hz,3H),7.24–7.21(m,7H),3.66(s,3H),3.38–3.35(m,2H),3.06–2.99(m,2H),2.32–2.26(m,4H),1.43–1.41(m,4H),1.39(s,9H),1.25–1.21(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.2,154.5,142.2,128.6,128.0,127.0,117.3,79.6,59.9,52.4,34.1,31.7,30.9,28.3,26.3 mass spectrometry data: MS (EI) 476.3 (M) + )。
Example 26: 6-cyano-4-methyl-2, 2-diphenylhexanoic acid methyl ester
Methyl 6-cyano-2,2,4-triphenylhexanoate
1, 1-stilbene (0.2 mmol), 2-methylcyclobutane-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 78% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.34–7.26(m,10H),3.68(s,3H),2.35(t,J＝5.1Hz,2H),2.26–2.08(m,2H),1.45–1.38(m,1H),1.28(dd,J＝7.5Hz,2H),0.63(d,J＝6.7Hz,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.5,143.1,142.9,128.9,128.8,128.0,127.9,127.0,126.9,119.7,60.0,52.3,44.7,33.2,29.4,20.2,14.7 mass spectrometry data: MS (EI) 321.2 (M) + )。
Example 27: 6-cyano-2, 4-triphenylhexanoic acid methyl ester
Methyl 6-cyano-2,2,4-triphenylhexanoate
1, 1-stilbene (0.2 mmol), 2-phenylcyclobutan-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then Sc is put intoThe hlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 19% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.34–7.26(m,10H),3.68(s,3H),2.35(t,J＝5.1Hz,2H),2.26–2.08(m,2H),1.45–1.38(m,1H),1.28(dd,J＝7.5Hz,2H),0.63(d,J＝6.7Hz,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.5,143.1,142.9,128.9,128.8,128.0,127.9,127.0,126.9,119.7,60.0,52.3,44.7,33.2,29.4,20.2,14.7 mass spectrometry data: MS (EI) 378 (M+);
example 28:4- (cyanomethoxy) -2, 2-diphenylbutanoic acid methyl ester
Methyl 4-(cyanomethoxy)-2,2-diphenylbutanoate
1, 1-stilbene (0.2 mmol), 3-oxocyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 66% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.32–7.28(m,6H),7.25–7.23(m,4H),4.07(s,2H),3.69(s,3H),3.36(t,J＝7.1Hz,2H),2.73(t,J＝7.2Hz,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.1,142.1,128.5,128.1,127.1,115.8,69.0,58.2,56.1,52.5,37.3 mass spectrometry data: MS (EI) 309.1 (M) + )。
Example 29:4- ((Boc) (cyanomethyl) amino) -2, 2-diphenylbutanoic acid methyl ester
Methyl 4-((tert-butoxycarbonyl)(cyanomethyl)amino)-2,2-diphenylbutanoate
1, 1-stilbene (0.2 mmol), 3- (((4- (trifluoromethyl) benzoyl) oxy) imino) azetidine-1-carboxylic acid tert-butyl ester (0.3 mmol), ir [ (dF (CF 3) ppy)]2 (dtbbpy) PF6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 74% yield. Nuclear magnetic data: 1 H NM R(400MHz,CDCl3)δ7.33–7.28(m,6H),7.25–7.23(m,4H),4.03(d,J＝50.8Hz,2H),3.71(s,3H),3.07–3.03(m,2H),2.62(s,2H),1.46(s,3H),1.37(s,6H). 13 c NMR (101 mhz, cdcl 3) delta 174.1,154.4,141.9,128.5,128.2,127.2,116.2,81.5,58.7,52.6,45.4,36.1,35.2,28.1 mass spectrometry data: MS (EI) 408.2 (M) + )。
Example 30:4- (cyanomethoxy) -2, 2-diphenylbutanoic acid methyl ester
Methyl 4-(2-cyanoethoxy)-2,2-diphenylpentanoate
1, 1-stilbene (0.2 mmol), 2-methyldihydrofuran-3 (2H) -one-O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 59% yield. Nuclear magnetic data 1 H NMR(400MHz,CDCl 3 )δ7.36(d,J＝7.6Hz,2H),7.31–7.28(m,6H),7.24–7.20(m,2H),3.65(s,3H),3.57–3.51(m,1H),3.10–3.05(m,2H),2.99–2.93(m,1H),2.43–2.37(m,2H),2.29(dd,J＝13.9,3.1Hz,1H),1.09(d,J＝6.0Hz,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.5,143.6,142.9,129.2,128.3,128.0,127.6,126.8,126.5,117.9,73.1,62.6,57.9,52.1,45.6,19.5,18.7 mass spectrometry data: MS (EI) 337.2 (M) + )。
Example 31:3- ((3-cyanomethyl) -1, 2-trimethylcyclopentyl) -2, 2-diphenylpropionic acid methyl ester
Methyl 3-(3-(cyanomethyl)-1,2,2-trimethylcyclopentyl)-2,2-diphenylpropanoate
1, 1-stilbene (0.2 mmol), 1, 7-trimethylbicyclo [2.2.0]heptane-O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 21% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.44(d,J＝7.0Hz,2H),7.38(d,J＝7.0Hz,2H),7.27–7.25(m,3H),7.23–7.20(m,4H,overlapped with CDCl 3 ),3.64(s,3H),2.65(d,J＝13.8Hz,1H),2.52(d,J＝13.8Hz,1H),2.39–2.34(m,1H),2.25–2.19(m,1H),2.17–2.11(m,1H),1.82–1.77(m,1H),1.25–1.11(m,2H),1.04(s,3H),0.82–0.77(m,1H),0.72(s,3H),0.46(s,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.5,145.2,144.6,129.1,128.9,127.8,127.8,126.6,126.6,120.0,57.1,52.1,47.6,46.8,44.1,44.0,32.7,28.7,23.5,20.3,19.7,18.7 mass spectrometry data: MS (EI) 389.2 (M) + )。
Example 32: 8-cyano-2, 4-triphenyloctanoic acid methyl ester
Methyl 8-cyano-2,2,4-triphenyloctanoate
1, 1-stilbene (0.2 mmol), 2-phenylcyclohexanone-O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature under irradiation of a 2X3W blue LEDMix for 12 hours. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 21% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.44(d,J＝7.0Hz,2H),7.38(d,J＝7.0Hz,2H),7.27–7.25(m,3H),7.23–7.20(m,4H,overlapped with CDCl 3 ),3.64(s,3H),2.65(d,J＝13.8Hz,1H),2.52(d,J＝13.8Hz,1H),2.39–2.34(m,1H),2.25–2.19(m,1H),2.17–2.11(m,1H),1.82–1.77(m,1H),1.25–1.11(m,2H),1.04(s,3H),0.82–0.77(m,1H),0.72(s,3H),0.46(s,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.5,145.2,144.6,129.1,128.9,127.8,127.8,126.6,126.6,120.0,57.1,52.1,47.6,46.8,44.1,44.0,32.7,28.7,23.5,20.3,19.7,18.7 mass spectrometry data: MS (EI) 389.2 (M) + )。
Example 33: 6-cyano-2, 2-diphenylhexanoic acid methyl ester
Methyl 6-cyano-2,2-diphenylhexanoate
1, 1-stilbene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), ir [ (dF (CF) 3 )ppy)] 2 (dtbbpy)PF 6 (2mol％,3.4mg)、Et 3 N (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Drying and concentrating under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 66% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.34–7.28(m,10H),3.71(s,3H),2.43–2.38(m,2H),2.27(t,J＝7.2Hz,2H),1.68-1.60(m,2H),1.26-1.19(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.5,142.4,128.7,127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8 mass spectrometry data: MS (EI) 307.2 (M) + )。
Example 34: 6-cyano-2, 2-diphenylhexanoic acid methyl ester
Methyl 6-cyano-2,2-diphenylhexanoate
1, 1-stilbene (0.2 mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), 2,4,5, 6-tetrakis (9-carbazolyl) -isophthalonitrile (2 mol%,3.1 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 53% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.34–7.28(m,10H),3.71(s,3H),2.43–2.38(m,2H),2.27(t,J＝7.2Hz,2H),1.68-1.60(m,2H),1.26-1.19(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.5,142.4,128.7,127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8 mass spectrometry data: MS (EI) 307.2 (M) + )。
Example 35: 6-cyano-2, 2-diphenylhexanoic acid methyl ester
Methyl 6-cyano-2,2-diphenylhexanoate
1, 1-stilbene (0.2 mmol), cyclobutanono- (4- (trifluoromethyl) benzoyl) oxime (0.3 mmol), tris (2, 2' -bipyridine) ruthenium bis (hexafluorophosphate) salt (2 mol%,3.4 mg), DIPEA (0.3 mmol) and DMSO (2.0 mL) were added to a 20mL Schlenk tube fitted with teflon caps. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds each) and CO was backfilled three times 2 (1 atm). Then, the Schlenk tube was stirred at room temperature for 12 hours under irradiation of a 2×3W blue LED. Thereafter, meI (0.8 mmol) was added to the reaction mixture, and the reaction mixture was stirred at 50℃for about 1 hour, then the reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2 mL. Times.6). Subsequently, the combined organic layers were subjected to anhydrous Na 2 SO 4 Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 5/1) to give the desired product in 51% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.34–7.28(m,10H),3.71(s,3H),2.43–2.38(m,2H),2.27(t,J＝7.2Hz,2H),1.68-1.60(m,2H),1.26-1.19(m,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 174.5,142.4,128.7,127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8 mass spectrometry data: MS (EI) 307.2 (M) + )。

Claims (5)

1. A process for preparing epsilon-, zeta-, eta-cyano carboxylic acids from carbon dioxide, characterized by: the method comprises the following steps: olefin and cyclic ketoxime are used as raw materials, iridium or ruthenium is used as a photocatalyst, and dimethyl sulfoxide is used as a solvent in the presence of a reducing agent; filling carbon dioxide gas after all the raw materials participating in the reaction are added, and reacting to obtain epsilon-, zeta-, eta-cyano carboxylic acid;
the reaction conditions are as follows: 2x3W blue LED, reacting for 12-24 hours at room temperature, then adding into an oil bath pot with methyl iodide at 50 ℃ for reacting for 1 hour;
the structural formula of the olefin is as follows:
r' R on the olefin is phenyl, methyl, naphthyl, thienyl or hydrogen; when R' and R are phenyl, the substituent groups are fluorine, chlorine, bromine, methoxy, ester groups and p-trifluoromethyl; r is R 1 Methyl or hydrogen;
the cyclic ketoxime has the following structural formula:
wherein R is on cyclic ketoxime 3 、R 4 、R 5 One selected from aryl, methyl, cyano, benzyl and ester; x is C, O, N; r is R 2 ＝p-CF 3 C 6 H 4 CO，n＝1，2，3；
The photocatalyst is bis [2- (2, 4-difluorophenyl) -5-trifluoromethylpyridine ] [2-2 '-bis (4-tert-butylpyridine) ] iridium bis (hexafluorophosphate), tris (2, 2' -bipyridine) ruthenium bis (hexafluorophosphate);
the reducing agent is DIPEA or triethylamine.
2. The process for producing an epsilon-, zeta-, eta-cyano carboxylic acid compound according to claim 1, wherein: the molar ratio of the olefin to the cyclic ketoxime is 1:1.5-2.0, the pressure of the carbon dioxide is 0.1MPa.
3. The process for producing an epsilon-, zeta-, eta-cyano carboxylic acid compound according to claim 1, wherein: the catalyst was used in an amount of 2mol% based on the number of moles of olefin.
4. The process for producing an epsilon-, zeta-, eta-cyano carboxylic acid compound according to claim 1, wherein: the molar ratio of the reducing agent to the olefin was 3.0:1.
5. the process for producing an epsilon-, zeta-, eta-cyano carboxylic acid compound according to claim 1, wherein: the molar ratio of methyl iodide to olefin is 4:1.
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* Cited by examiner, † Cited by third party
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A dual photoredox-nickel strategy for remote functionalization via iminyl radicals: radical ring-opening-arylation, -vinylation and -alkylation cascades;Elizabeth M Dauncey 等;《Chemical science》;第10卷(第33期);第7728-7733页 *
Iron‐Catalyzed Ring‐Opening/Allylation of Cyclobutanone Oxime Esters with Allylic Sulfones;Zhao, JF 等;《Advanced Synthesis & Catalysis》;第360卷(第9期);第1775-1779页 *
Synthesis of Functionalized Nitriles by Microwave-Promoted Fragmentations of Cyclic Iminyl Radicals;Mary M. Jackman 等;《Chemistry - A European Journal》;第24卷(第3期);第594-598页 *
Visible-Light Photoredox-Catalyzed Ring-Opening Carboxylation of Cyclic Oxime Esters with CO2;Yuan-Xu Jiang 等;《ChemSusChem》;第13卷(第23期);第6312-6317页 *

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