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

Abstract

The invention relates to the fields of medicine, organic chemical industry and fine chemical industry, in particular to a method for preparing ε-, ζ-, η-cyanocarboxylic acids from carbon dioxide. Using olefins and cyclic ketoxime as raw materials, iridium, 4CZIPN or ruthenium as catalysts, in the presence of a reducing agent, dimethyl sulfoxide as a solvent, 2x3W blue LEDs, react at room temperature for 12 to 24 hours, then add methyl iodide and carry out a synthesis reaction in an oil bath at 50°C for 1 hour to obtain the product. After the reaction, a series of ε-, ζ-, η-cyanocarboxylic acid compounds can be obtained in high yield after simple post-treatment. Stilbenes with various substituents and cyclic ketoximes with various substituents can be used as reaction substrates to obtain the corresponding ε-, ζ-, η-cyanocarboxylic acid compounds.

Description

A method for preparing ε-, ζ-, η-cyanocarboxylic acids from carbon dioxide

technical field

The present invention relates to the fields of medicine, organic chemical industry and fine chemical industry, in particular to a simple and efficient method for synthesizing ε-, ζ-, η-cyanocarboxylic acid compounds catalyzed by iridium, 4CzIPN or ruthenium, using carbon dioxide, olefins and cyclic ketone oxime as raw materials, using DIPEA or triethylamine as reducing agent, and DMSO as solvent.

Background technique

Cyanocarboxylic acids are a class of important biologically active compounds, and are also important intermediates for the construction of vitamin B6, caffeine, folic acid and other drug molecules (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-cyanocyclohexaneacetic, WO 2004111256A1, 20041223.). In addition, the cyano group in its structure can be hydrolyzed into a carboxyl group, and the resulting aliphatic dicarboxylic acid compound is widely used in polymer polymerization reactions and is an important monomer for the synthesis of polyamides and polyesters. Therefore, the effective synthesis of such compounds has strong 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.; Jackstell, R.; Beller, M. Angew. Chem. Int. Ed. 2020, 59, 20394–20398.). The classic synthetic method of this kind of compound is to utilize the nucleophilic substitution reaction of halogenated carboxylic acid and sodium cyanide or hydrocyanic acid to prepare, yet need to use highly toxic sodium cyanide or hydrocyanic acid in this method, has brought great trouble to practical operation; In addition, through the single cyano group hydrolysis reaction of dinitrile compound, also is a class of important method of preparing cyano carboxylic acid, but two cyano groups have similar reactivity in the compound, how to control reaction conditions, guarantees that only one cyano group is hydrolyzed, is a challenging work (see: Zhu, D .; MukherJee, C.; Biehl, E.R.; Hua, L. Adv. Synth. Catal. 2007, 349, 1667–1670.).

Recently, Professor Yu Dagang reported that a series of cyanocarboxylic acids can be obtained through the ring-opening carboxylation of cyclic ketoxime esters with carbon dioxide. However, this reaction is limited to 2-aryl substituted cyclic ketoxime esters, and the scope of substrate application is narrow, and the synthesis of substrates is difficult (see: Jiang, Y.-X.; Chen, L.; Ran, C.-K.; Song, L.; Zhang, W.; Liao, L.-L.; Yu, D.-G. ChemSus Chem 2020, 13, 6312–6317.). It is of high research value to further develop the method of using simple and easy-to-obtain raw materials and mild reaction conditions to realize the rapid construction of cyanocarboxylic acid compounds with different carbon chain lengths.

Contents of the invention

In view of the deficiencies in the background technology, the present invention uses cheap and readily available carbon dioxide, olefins, and cyclic ketone oximes (2-, 3-, and 3,3,-substituted cyclobutanone oxime, cyclopentanone oxime, cyclohexanone oxime, etc.) as starting materials, and under the promotion of visible light, under the catalysis of iridium, 4CZIPN or ruthenium, a series of ε-, ζ-, η-cyanocarboxylic acids are synthesized through continuous free radical addition/one-electron reduction/carboxylation reactions. The method of the invention has wide sources of raw materials, simple operation method, easy separation and purification, and high yield.

The synthesis method of the ε-, ζ-, η-cyanocarboxylic acid compound of the present invention is as follows: olefins and cyclic ketoxime are used as raw materials, iridium, 4CZIPN or ruthenium are used as photocatalysts, with the participation of a reducing agent, dimethyl sulfoxide is used as a solvent, and after all the raw materials participating in the reaction are added, carbon dioxide gas is charged to carry out the reaction to obtain a series of cyanocarboxylic acid compounds.

The specific technological process of this reaction is as follows:

R' on the olefin, R is phenyl, methyl, naphthyl, thienyl or hydrogen; R', when R is phenyl, its substituents are fluorine, chlorine, bromine, methoxy, ester group and p-trifluoromethyl; ^R1 is methyl or hydrogen.

The structural formula of the raw material olefin used is: R' on the olefin, R is phenyl, methyl, naphthyl, thienyl or hydrogen; R', when R is phenyl, its substituents are fluorine, chlorine, bromine, methoxy, ester and p-trifluoromethyl; ^R1 is methyl or hydrogen.

The cyclic ketoxime is selected from four-membered rings, six-membered rings, heterocyclic rings and their different substituent products.

The structural formula of the raw material cyclic ketoxime used is: R ³ , R ⁴ , and R ⁵ on the cyclic ketoxime are selected from one of aryl, methyl, cyano, benzyl, and ester; X is C, O, N; R ² =p-CF ₃ C ₆ H ₄ CO, n=1,2,3.

The specific reaction conditions of the present invention are: 2x 3W blue LEDs, room temperature for 12 to 24 hours, then add methyl iodide in a 50°C oil bath and react for another hour.

The photocatalyst used in the above reaction is bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium bis(hexafluorophosphate) salt, three(2,2'-bipyridyl)ruthenium bis(hexafluorophosphate)salt, 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, and the consumption of the catalyst is 2mol% of the olefin moles;

The molar ratio of olefin to cyclic ketoxime used is 1:1.5, and the pressure of carbon dioxide is 0.1MPa;

The reducing agent used is N,N-diisopropylethylamine (DIPEA) or triethylamine (Et ₃ N); the molar ratio of it to olefin is 3.0:1.

The molar ratio of iodomethane to olefin is 4:1.

The post-reaction treatment is simple and simple, and pure ε-, ζ-, η-cyanocarboxylic acid compounds can be obtained only by a simple column chromatography separation method using a mixed solvent of petroleum ether and ethyl acetate as an eluent.

The raw material olefin and cyclic ketoxime used in the present invention were synthesized according to the literature (Cheng, Z.; Jin, W.; Liu, CB 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.2 017, 56, 12727–12731.).

Beneficial effect:

The invention provides a more concise and feasible way to synthesize a series of ε-, ζ-, η-cyanocarboxylic acid compounds by using olefin and cyclic ketone oxime for the first time, and has important application value.

Detailed ways

Below in conjunction with embodiment the present invention is described in detail, each embodiment of the present invention reacts as follows:

Example 1 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 (2 mol%, 3.4 mg), DIPEA (0.3 mmol), and DMSO (2.0 mL) were added to a 20 mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： 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 )δ174.5,142.4,128.7,127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8.质谱数据：MS(EI):307.2(M ⁺ )。

Example 2 Methyl 6-cyano-2-phenyl-2-(p-tolyl)hexanoate

Methyl 6-cyano-2-phenyl-2-(p-tolyl)hexanoate

1-Methyl-4-(1-phenylethenyl)benzene (0.2mmol), cyclobutanone O-(4-(trifluoromethyl)benzoyl)oxime (0.3mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube equipped with Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 60% yield.核磁数据： 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(101MHz,CDCl3))δ174.64,142.61,139.38,136.53,128.66,128.63,128.56,127.88,126.79,119.53,59.78,52.35,37.33,25.78,24.56,20.89,16.87.质谱数据：MS(EI):321.2(M ⁺ )。

Example 3: Methyl 6-cyano-2-(4-methoxyphenyl)-2-phenylhexanoate

Methyl 6-cyano-2-(4-methoxyphenyl)-2-phenylhexanoate

1-Methoxy-4-(1-phenylethenyl)benzene (0.2mmol), cyclobutanone O-(4-(trifluoromethyl)benzoyl)oxime (0.3mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube equipped with Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 68% yield.核磁数据： 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 )δ174.7,158.3,142.8,134.3,129.8,128.6,127.9,126.8,119.5,113.2,59.4,55.1,52.3,37.4,25.8,24.6,16.9.质谱数据：MS(EI):337.2(M ⁺ )。

Example 4: Methyl 6-cyano-2-(4-fluorophenyl)-2-phenylhexanoate

Methyl 6-cyano-2-(4-fluorophenyl)-2-phenylhexanoate

1-Fluoro-4-(1-phenylethenyl)benzene (0.2mmol), cyclobutanone O-(4-(trifluoromethyl)benzoyl)oxime (0.3mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube equipped with Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 56% yield.核磁数据： 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(101MHz,CDCl3)δ174.3,142.3,130.4,130.4,128.5,128.1,127.0,114.9,114.6,59.6,52.5,37.4,25.7,24.5,16.9.质谱数据：MS(EI):325.2(M ⁺ )。

Example 5: Methyl 2-(4-chlorophenyl)-6-cyano-2-phenylhexanoate

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 20 mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 59% yield.核磁数据： 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 )δ174.1,142.1,141.1,132.8,130.2,128.5,128.1,128.1,127.1,119.4,59.7,52.5,37.2,25.7,24.5,16.9.质谱数据：MS(EI):341.1(M ⁺ )。

Example 6: Methyl 2-(4-bromophenyl)-6-cyano-2-phenylhexanoate

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 20 mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： 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 )δ173.9,141.9,141.6,131.0,130.5,128.4,128.1,127.1,121.0,119.4,59.7,52.5,37.1,25.6,24.5,16.8.质谱数据：MS(EI):385.1(M ⁺ )。

Example 7: Methyl 6-cyano-2-phenyl-2-(4-(trifluoromethyl)phenyl)hexanoate

Methyl 6-cyano-2-phenyl-2-(4-(trifluoromethyl)phenyl)hexanoate

1-(1-Phenylvinyl)-4-(trifluoromethyl)benzene (0.2mmol), cyclobutanone O-(4-(trifluoromethyl)benzoyl)oxime (0.3mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to 20mL Schlenk Tubes, fitted with Teflon caps. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 44% yield.核磁数据： 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 )δ173.8,141.7,129.2,128.5,128.2,127.3,124.9,124.8,119.4,60.1,52.6,37.2,25.7,24.5,16.9.质谱数据：MS(EI):375.1(M ⁺ )。

Example 8: Methyl 6-cyano-2-phenyl-2-(m-tolyl)hexanoate

Methyl 6-cyano-2-phenyl-2-(m-tolyl)hexanoate

1-Methyl-3-(1-phenylethenyl)benzene (0.2mmol), cyclobutanone O-(4-(trifluoromethyl)benzoyl)oxime (0.3mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube equipped with Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 59% yield.核磁数据： 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 )δ174.6,142.5,142.4,137.5,129.2,128.7,127.9,127.8,127.6,126.9,125.8,119.5,60.0,52.3,37.3,25.8,24.6,21.6,16.8.质谱数据：MS(EI):321.2(M ⁺ )。

Example 9: Methyl 2-(2-chlorophenyl)-6-cyano-2-phenylhexanoate

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 20 mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 66% yield.核磁数据： 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 )δ174.1,140.2,134.1,131.0,130.9,128.9,128.3,128.1,127.3,126.1,59.2,52.5,33.1,25.6,24.2,16.9.质谱数据：MS(EI):282.1(M ⁺ )。

Example 10: Methyl 6-cyano-2-(2,4-dichlorophenyl)-2-phenylhexanoate

Methyl 6-cyano-2-(2,4-dichlorophenyl)-2-phenylhexanoate

2,4-Dichloro-1-(1-phenylethenyl)benzene (0.2 mmol), cyclobutanone O-(4-(trifluoromethyl)benzoyl)oxime (0.3 mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube , with Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 67% yield.核磁数据： 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 )δ173.7,139.0,138.9,134.8,133.4,131.9,130.6,128.8,128.3,127.5,126.4,119.3,58.9,52.6,33.1,25.6,24.2,16.9.质谱数据：MS(EI):375.1(M ⁺ )。

Example 11: Methyl 6-cyano-2,2-di-p-tolylhexanoate

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 20 mL of Sch Lenk tubes, fitted with Teflon caps. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 62% yield.核磁数据： 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(101MHz,CDCl3)δ174.8,139.5,136.4,128.6,128.5,119.6,77.3,77.00,76.7,59.5,52.3,37.4,25.8,24.6,20.9,16.9.质谱数据：MS(EI):335.2(M+)。

Example 12: Methyl 2,2-bis(4-chlorophenyl)-6-cyanohexanoate

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) were added to 20 mL of Sch Lenk tubes, fitted with Teflon caps. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： 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 )δ173.7,140.7,133.1,130.0,128.3,119.4,59.3,52.7,37.2,25.7,24.5,16.9.质谱数据：MS(EI):375.1(M ⁺ )。

Example 13: Methyl 6-cyano-2-(naphthalen-2-yl)-2-phenylhexanoate

Methyl 6-cyano-2-(naphthalen-2-yl)-2-phenylhexanoate

2- (1-phenyl ethylene) 萘 (0.2 mmol), cytotosor O- (4- (trifluorophyl) benzol) 肟 (0.3 mmol), IR [(DF (CF ₃ ) PPY)] ₂ (DTBBPY) PF ₆ (2mol %, 3.4 mg), DIPEA (0.3 mmol), and DMSO, and DMSO (2.0ml) Add to the 20ml SCHLENK tube with Teflon hat. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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 82% yield.核磁数据： 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 )δ174.3,142.4,139.7,132.7,132.1,128.7,128.1,128.0,127.5,127.3,127.2,127.1,126.9,126.1,126.1,119.5,60.1,52.4,37.20,25.7,24.6,16.8.质谱数据：MS(EI):357.2(M ⁺ )。

Example 14: Methyl 6-cyano-2-phenyl-2-(thiophen-2-yl)hexanoate

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 20 mL Schlenk tube fitted with a Teflon cap . The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 56% yield.核磁数据： 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 )δ173.6,145.8,142.8,128.1,127.4,127.2,127.0,126.2,125.1,119.4,57.8,52.6,39.1,25.6,24.6,16.9.质谱数据：MS(EI):313.1(M ⁺ )。

Example 15: Methyl (R)-6-cyano-3-methyl-2,2-diphenylhexanoate

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 20 mL Schlenk tube fitted with a Teflon cap . The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： ¹ H NMR(400MHz,CDCl ₃ )δ7.31–7.24(m,11H,overlappedwith 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 )δ174.6,127.5,126.9,126.9,119.6,65.6,52.3,35.5,29.7,24.0,17.3.质谱数据：MS(EI):321.2(M ⁺ )。

Example 16: Methyl 6-cyano-2-methyl-2-(naphthalen-2-yl)hexanoate

Methyl 6-cyano-2-methyl-2-(naphthalen-2-yl)hexanoate

2- (1-methyl ethylene) 萘 (0.2 mmol), cytotosor O- (4- (trifluorophyl) benzol) 肟 (0.3 mmol), IR [(DF (CF ₃ ) PPY)] ₂ (DTBBPY) PF ₆ (2mol %, 3.4 mg), DIPEA (0.3mmol), and DMSO ( 2.0ml) Add to the 20ml SCHLENK tube with Teflon hat. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 25% yield.核磁数据： 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 )δ176.5,140.5,133.2,132.2,128.2,128.0,127.4,126.2,126.0,124.4,124.3,119.5,52.3,50.1,38.4,25.8,23.9,22.4,17.0.质谱数据：MS(EI):295.2(M ⁺ )。

Example 17: (S)-methyl 4-(6-cyano-1-methoxy-1-oxohex-2-yl)benzoate

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 20 mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 72% yield.核磁数据： 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 )δ173.4,166.7,143.6,130.0,129.3,127.8,119.3,52.2,52.1,51.2,32.4,26.5,25.0,16.9.质谱数据：MS(EI):289.1(M ⁺ )。

Example 18: Dimethyl 5-(cyanomethyl)-2,2-diphenyladipate

Dimethyl 5-(cyanomethyl)-2,2-diphenylhexanedioate

1,1-Stilbene (0.2mmol), methyl 3-(((4-(trifluoromethyl)benzoyl)oxy)imino)cyclobutane-1-carboxylate (0.3mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to 20mL Sch Lenk tubes, fitted with Teflon caps. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 60% yield.核磁数据： 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 )δ172.7,142.1,142.0,128.6,128.6,128.0,127.0,59.9,52.5,52.3,41.6,34.9,27.2,19.1.质谱数据：MS(EI):365.2(M ⁺ )。

Example 19: Methyl 6-cyano-2,2,5-triphenylhexanoate

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 20 mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 77% yield.核磁数据： 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 )δ174.4,142.3,142.2,141.0,128.7,128.6,127.9,127.9,127.4,127.2,126.9,126.8,118.2,60.0,52.3,42.4,35.7,30.2,25.3.质谱数据：MS(EI):383.2(M ⁺ )。

Example 20: Methyl 5-benzyl-6-cyano-2,2-diphenylhexanoate

Methyl 5-benzyl-6-cyano-2,2-diphenylhexanoate

1,1-Stilbene (0.2mmol), 3-benzylcyclobutan-1-one O-(4-(trifluoromethyl)benzoyl)oxime (0.3mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol), and DMSO (2.0mL) were added to a 20mL Schlenk tube equipped with Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： 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 )δ174.4,142.4,142.3,138.6,128.9,128.7,128.6,128.5,127.9,127.9,126.9,126.9,126.4,118.3,60.1,52.4,39.4,37.7,35.5,29.0,20.9.质谱数据：MS(EI):397.2(M ⁺ )。

Example 21: Methyl 5-(Benzyloxy)-6-cyano-2,2-diphenylhexanoate

Methyl 5-(benzyloxy)-6-cyano-2,2-diphenylhexanoate

1,1-Stilbene (0.2mmol), 3-benzyloxycyclobutan-1-one O-(4-(trifluoromethyl)benzoyl)oxime (0.3mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol), and DMSO (2.0mL) were added to a 20mL Schlenk tube equipped with Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 50% yield.核磁数据： 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 )δ174.4,142.4,142.1,137.4,128.8,128.7,128.4,128.0,127.9,127.8,127.0,126.9,117.5,74.4,71.6,59.9,52.4,33.1,29.5,22.8.质谱数据：MS(EI):413.2(M ⁺ )。

Example 22: Methyl 5-(((Benzyloxy)carbonyl)amino)-6-cyano-2,2-diphenylhexanoate

Methyl 5-(((benzyloxy)carbonyl)amino)-6-cyano-2,2-diphenylhexanoate

1,1-Stilbene (0.2mmol), benzyl (3-(((4-(trifluoromethyl)benzoyl)oxy)imino)cyclobutyl)carbamate (0.3mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy)· _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to 20mL Schlenk tubes, fitted with Teflon caps. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 39% yield.核磁数据： 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 )δ174.4,155.8,142.3,142.1,136.0,128.6,128.6,128.5,128.5,128.2,128.2,128.1,128.1,128.1,128.0,127.1,127.1,117.0,66.9,59.9,52.6,48.2,43.6,34.6,29.5,25.0,23.8,19.4.质谱数据：MS(EI):456.2(M ⁺ )。

Example 23: Methyl 5,6-dicyano-2,2-diphenylhexanoate

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 20 mL Schlenk tube equipped with Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 80% yield.核磁数据： 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 )δ174.0,141.7,141.7,128.5,128.5,128.2,128.2,127.3,118.7,115.4,59.7,52.6,35.3,28.6,27.7,20.7.质谱数据：MS(EI):332.2(M ⁺ )。

Example 24: Methyl 6-cyano-5-methyl-2,2,5-triphenylhexanoate

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( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube equipped with Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 70% yield.核磁数据： 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.质谱数据：MS(EI):397.2(M ⁺ )。

Example 25: tert-butyl 4-(cyanomethyl)-4-(4-methoxy-4-oxo-3,3-diphenylbutyl)piperidine-1-carboxylate

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) Add to 20mL Schlenk tubes fitted with Teflon caps. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 76% yield.核磁数据： 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 )δ174.2,154.5,142.2,128.6,128.0,127.0,117.3,79.6,59.9,52.4,34.1,31.7,30.9,28.3,26.3.质谱数据：MS(EI):476.3(M ⁺ )。

Example 26: Methyl 6-cyano-4-methyl-2,2-diphenylhexanoate

Methyl 6-cyano-2,2,4-triphenylhexanoate

1,1-Stilbene (0.2 mmol), 2-methylcyclobutan-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 20 mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 78% yield.核磁数据： 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 )δ174.5,143.1,142.9,128.9,128.8,128.0,127.9,127.0,126.9,119.7,60.0,52.3,44.7,33.2,29.4,20.2,14.7.质谱数据：MS(EI):321.2(M ⁺ )。

Example 27: Methyl 6-cyano-2,2,4-triphenylhexanoate

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 20 mL Schlenk tube equipped with a Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： 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 )δ174.5,143.1,142.9,128.9,128.8,128.0,127.9,127.0,126.9,119.7,60.0,52.3,44.7,33.2,29.4,20.2,14.7.质谱数据：MS(EI):378(M+)；

Example 28: Methyl 4-(cyanomethoxy)-2,2-diphenylbutyrate

Methyl 4-(cyanomethoxy)-2,2-diphenylbutanoate

Add 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) to a 20 mL Schlenk tube fitted with a Teflon cap . The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 66% yield.核磁数据： 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 )δ174.1,142.1,128.5,128.1,127.1,115.8,69.0,58.2,56.1,52.5,37.3.质谱数据：MS(EI):309.1(M ⁺ )。

Example 29: Methyl 4-((tert-butoxycarbonyl)(cyanomethyl)amino)-2,2-diphenylbutyrate

Methyl 4-((tert-butoxycarbonyl)(cyanomethyl)amino)-2,2-diphenylbutanoate

1,1-Stilbene (0.2mmol), 3-(((4-(trifluoromethyl)benzoyl)oxy)imino)azetidine-1-carboxylate tert-butyl ester (0.3mmol), Ir[(dF(CF3)ppy)]2(dtbbpy)·PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to 20mL Sch Lenk tubes, fitted with Teflon caps. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： 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(101MHz,CDCl3)δ174.1,154.4,141.9,128.5,128.2,127.2,116.2,81.5,58.7,52.6,45.4,36.1,35.2,28.1.质谱数据：MS(EI):408.2(M ⁺ )。

Example 30: Methyl 4-(cyanomethoxy)-2,2-diphenylbutyrate

Methyl 4-(2-cyanoethoxy)-2,2-diphenylpentanoate

1,1-Stilbene (0.2mmol), 2-methyldihydrofuran-3(2H)-one-O--(4-(trifluoromethyl)benzoyl)oxime (0.3mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to 20mL Sch Lenk tubes, fitted with Teflon caps. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (PE/EA 5/1) to give the desired product in 59% yield.核磁数据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 CNMR(101MHz,CDCl ₃ )δ174.5,143.6,142.9,129.2,128.3,128.0,127.6,126.8,126.5,117.9,73.1,62.6,57.9,52.1,45.6,19.5,18.7.质谱数据：MS(EI):337.2(M ⁺ )。

Example 31: Methyl 3-((3-cyanomethyl)-1,2,2-trimethylcyclopentyl)-2,2-diphenylpropionate

Methyl 3-(3-(cyanomethyl)-1,2,2-trimethylcyclopentyl)-2,2-diphenylpropanoate

1,1-Stilbene (0.2mmol), 1,7,7-Trimethylbicyclo[2.2.0]heptane-O-(4-(trifluoromethyl)benzoyl)oxime (0.3mmol), Ir[(dF( _CF3 )ppy)] ₂ (dtbbpy) _PF6 (2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to 2 0 mL Schlenk tubes with Teflon caps. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： 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 )δ174.5,145.2,144.6,129.1,128.9,127.8,127.8,126.6,126.6,120.0,57.1,52.1,47.6,46.8,44.1,44.0,32.7,28.7,23.5,20.3,19.7,18.7.质谱数据：MS(EI):389.2(M ⁺ )。

Example 32: Methyl 8-cyano-2,2,4-triphenyloctanoate

Methyl 8-cyano-2,2,4-triphenyloctanoate

Add 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) to a 20 mL Schlenk tube fitted with a Teflon cap . The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： 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 )δ174.5,145.2,144.6,129.1,128.9,127.8,127.8,126.6,126.6,120.0,57.1,52.1,47.6,46.8,44.1,44.0,32.7,28.7,23.5,20.3,19.7,18.7.质谱数据：MS(EI):389.2(M ⁺ )。

Example 33: Methyl 6-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), Et ₃ N (0.3 mmol), and DMSO (2.0 mL) were added to a 20 mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： 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 )δ174.5,142.4,128.7,127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8.质谱数据：MS(EI):307.2(M ⁺ )。

Example 34: Methyl 6-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), 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 20 mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： 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 )δ174.5,142.4,128.7,127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8.质谱数据：MS(EI):307.2(M ⁺ )。

Example 35: Methyl 6-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), tris(2,2'-bipyridyl)ruthenium bis(hexafluorophosphate) salt (2 mol%, 3.4 mg), DIPEA (0.3 mmol), and DMSO (2.0 mL) were added to a 20 mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about -0.1 MPa (last 30 seconds each) and backfilled with _CO2 (1 atm) in three installments. Then, the Schlenk tube was stirred at room temperature under 2 × 3W blue LED illumination for 12 h. After that, MeI (0.8 mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 °C 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). Then, the combined organic layers were dried over anhydrous Na ₂ SO ₄ 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.核磁数据： 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 )δ174.5,142.4,128.7,127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8.质谱数据：MS(EI):307.2(M ⁺ )。

Claims (5)

1. A method for preparing ε-, ζ-, η-cyanocarboxylic acid by carbon dioxide, is characterized in that: the method is: with olefin and cyclic ketone oxime as raw material, iridium or ruthenium as photocatalyst, under the participation of reducing agent, dimethyl sulfoxide is made solvent; All raw materials participating in the reaction are charged with carbon dioxide gas after adding, react, obtain ε-, ζ-, η-cyanocarboxylic acid; The reaction conditions are: 2x 3W blue LEDs, react at room temperature for 12-24 hours, then add methyl iodide in a 50°C oil bath and react for another hour; Alkenes have the following structural formula: R' on the olefin, R is phenyl, methyl, naphthyl, thienyl or hydrogen; R', when R is phenyl, its substituents are fluorine, chlorine, bromine, methoxy, ester group and p-trifluoromethyl; ^R1 is methyl or hydrogen; The structural formula of cyclic ketoxime is as follows: Wherein, R ³ , R ⁴ , and R ⁵ on cyclic ketoxime are selected from one of aryl, methyl, cyano, benzyl, and ester; X is C, O, N; 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'-bi(4-tert-butylpyridine)]iridium bis(hexafluorophosphate) salt, tris(2,2'-bipyridyl)ruthenium bis(hexafluorophosphate) salt; The reducing agent is DIPEA or triethylamine. 2. The method for preparing ε-, ζ-, η-cyanocarboxylic acid compounds according to claim 1, characterized in that: the molar ratio of the alkene to cyclic ketone oxime is 1:1.5-2.0, and the pressure of carbon dioxide is 0.1MPa. 3. The method for preparing ε-, ζ-, η-cyanocarboxylic acid compounds according to claim 1, characterized in that: the amount of the catalyst is 2mol% of the moles of olefins. 4. The method for preparing ε-, ζ-, η-cyanocarboxylic acid compounds according to claim 1, characterized in that: the molar ratio of the reducing agent to the olefin is 3.0:1. 5. The method for preparing ε-, ζ-, η-cyanocarboxylic acid compounds according to claim 1, characterized in that: the molar ratio of methyl iodide to olefins is 4:1.