A photoactive nitrene organic small molecule photocatalyst and its preparation method and application

Abstract

The present invention discloses a photoactive nitrene-based organic small molecule photocatalyst, its preparation method, and application. The present invention utilizes nitrene compounds as organic photocatalysts to achieve free radical addition reactions between alkyl chlorides and organic selenium ether compounds under the action of visible light, resulting in highly selective synthesis of a series of organoselenium compounds with potential pharmaceutical activity. This method provides a simple, efficient, and highly selective synthesis pathway for organoselenium compounds. The method catalyzes Giese-type (cyclo)addition reactions, Heck-type coupling reactions, and Minisci-type aromatic ring reactions of unsaturated carbon-carbon double bonds. This method does not require the involvement of transition metals and utilizes readily available nitrene salts as photocatalysts, resulting in a novel method.

Description

Technical Field

[0001] The present invention belongs to the field of organic synthesis, and in particular relates to a photoactive nitrene organic small molecule photocatalyst and a preparation method and application thereof. Background Art

[0002] N-heterocyclic carbenes (NHCs) have been shown to be among the most powerful ligands and organocatalysts in organic synthesis due to their unique donor and steric structural properties. In recent years, they have been further applied in photo / NHC-coupled dual catalytic systems. However, the development of N-heterocyclic nitrile (NHN) cations, which are isoelectronic and isostructural analogs of NHCs, is still in its infancy. Until recently, their catalytic ability has only been demonstrated in hindered Lewis acid-base pair (FLP) catalysis.

[0003] NHNs have a lone pair and a vacant pπ orbital, exhibiting amphoteric behavior and possessing many attractive properties, such as stability, low cost, low toxicity, and ready availability. In 2017, Gandelman and colleagues first demonstrated the electron-accepting properties of NHNs by forming stable Lewis acid / base adducts with various phosphines (A. Pogoreltsev, Y. Tulchinsky, N. Fridman, M. Gandelman, J. Am. Chem. Soc. 2017, 139, 4062–4067). Subsequently, the research groups of Stephan, Mehta, Goicoechea, and Gandelman further exploited their Lewis acidity, opening new opportunities for FLP activation of SS and Si-H bonds. In the context of developing NHN cationic Lewis acids, other nitrogen ions have also been explored by the research groups of Osuka, Stephan, Kütt, and Reed. However, despite these recent impressive reports, the novel properties of NHNs in catalysis remain relatively unexplored.

[0004] Alkyl chlorides are abundant, inexpensive, readily available, structurally diverse, and relatively safe raw materials. Their selective transformation is a challenging task, as their single-electron reducibility has been shown to transform them into value-added compounds. In this context, photoredox catalysis is used to generate alkyl radicals from alkyl chlorides, followed by subsequent functionalization reactions. Most current processes rely on the strong redox potential of photosensitizers or the use of excited-state photosensitizers (JMR Narayanam, JW Tucker, CRJ Stephenson, J. Am. Chem. Soc. 2009, 131, 8756–8757; T. Maji, A. Karmakar, O. Reiser, J. Org. Chem. 2011, 76, 736–739; M. Neumann, S. Füldner, B. K.Zeitler,Angew. Chem.Int.Ed.2011,50,951–954;M.Pirtsch,S.Paria,T.Matsuno,H.Isobe,O.Reiser,Chem.-Eur.J.2012,18,7336–7340;H.Yin,SJmchemnaCarro Chem.Soc.2015,137,9234–9237;R.Matsubara,T.Yabuta,U.Md Idros,M.Hayashi,F.Ema,Y.Kobori,K.Sakata,J.Org.Chem.2018,83,9381–9390;g)Y.Li,Z.Ye,Y.-M.Lin, Y.Liu,Y.Zhang,L.Gong,Nat.Commun.2021,12,2894.)Please log in on metallaphot H. Shimakoshi, M. Tokunaga, T. Baba, Y. Hisaeda, Chem.Commun.2004,1806–1807;K.Tahara,Y.Hisaeda,Green Chem.2011,13,558–561;H.Tian,H.Shimakoshi,G.Park,S.Kim,Y.You,Y.Hisaeda,Dalton Trans.2018,47,675–683;M.Claros,F.Ungeheuer,F.Franco,V.Martin-Diaconescu,A.Casitas,J. Lloret-Fillol,Angew.Chem.Int.Ed.2019,58,4869–4874;HASakai,W.Liu,CCLe,DWCMacMillan,J.Am.Chem.Soc.2020,142,11691–116-Sch97,MAitzer (EDBeato,EDBeato,P.Melchiorre,Nat.Chem.2019,11,129–135;T.Constantin,M.Zanini,A.Regni,NSSheikh,F.Juliá,D.Leonori,Science.2020,367,1021(102)Despite the value and utility of these strategies, they more or less suffer from the problems of high catalyst cost and complex catalytic cycle, requiring suitable photocatalysts, transition metals, ligands, additives or other parameters to complete the catalytic cycle.

[0005] On the other hand, organic selenium compounds possess important physiological effects, including antioxidant, anticancer, heart and liver protection, immune enhancement, and reproductive enhancement. Many compounds containing this skeleton exhibit significant biological activity (G. Mugesh, W.-W. Du Mont, H. Sies, Chem. Rev. 2001, 101, 2125–2180; C. W. Nogueira, G. Zeni, J. B. Rocha, Chem. Rev. 2004, 104, 6255–6286). Organic selenium is the primary form of selenium in living organisms, primarily as selenoamino acids such as selenomethionine, selenocysteine, and selenocysteine, as well as selenoproteins (in which selenium is primarily present as selenocysteine ​​and selenomethionine residues). Organic selenium has high bioavailability and certain physiological activities, making it closely related to metabolism. Currently, only selenoproteins containing selenocysteine ​​residues, approximately 20 in number, are capable of exerting physiological functions in mammals. One of the most widely studied and important enzymes is glutathione peroxidase (GPx) (JT Rotruck; L. Pope A.; HE Ganther; A. Swanson; DG Hefeman; W. Hoekstra Science. 1973, 179, 588). For example, sheep raised in areas where the soil is deficient in selenium suffer from "white muscle disease." Selenium deficiency can weaken the immune system, making it easier for viruses and pathogens to invade the body, leading to conditions such as Keshan disease and Kashin-Beck disease. In addition to the important role of selenium in living organisms described above, the application of selenium-containing compounds in biochemistry is also gradually being developed. New synthetic pathways for organic selenium compounds are needed. Summary of the Invention

[0006] The purpose of the present invention is to provide a photoactive nitrene compound organic small molecule photocatalyst and its preparation method and application. The present invention uses nitrene compounds as organic photocatalysts for the first time to realize the free radical addition reaction of alkyl chloride and organic selenium ether compounds under the action of visible light, and highly selectively synthesizes a series of organic selenium compounds with potential pharmaceutical activity. This method provides a simple, efficient and highly selective synthesis route for organic selenium compounds.

[0007] In the first aspect, the nitrene compound provided by the present invention is a compound having a structural formula as shown in Formula I, Formula II or Formula III.

[0008]

[0009] Among them, R 1 、R 2 and R 3 each independently selected from methyl, ethyl, isopropyl or phenyl;

[0010] R 4- Selected from iodide, triflate or tetrafluoroborate.

[0011] Preferably, the compound represented by formula I is a compound represented by formula IA or a compound represented by formula IB:

[0012]

[0013] In formula IA, R 1 is selected from methyl, ethyl, isopropyl or phenyl;

[0014] In formula IB, R 4- Selected from trifluoromethanesulfonate or tetrafluoroborate.

[0015] As an example, the compound represented by formula I is any one of the following compounds:

[0016] Formula I-1: R 1 =Me;R 4- =I - ;

[0017] Formula I-2: R 1 =Et; R 4- =I - ;

[0018] Formula I-3: R 1 =i-Pr; R 4- =I - ;

[0019] Formula I-4: R 1 =Ph; R 4- =I - ;

[0020] Formula I-5: R 1 =Me;R 4- =OTf - ;

[0021] Formula I-6: R 1 =Me;R 4- =BF4 - .

[0022] As an example, the compound represented by formula II is any one of the following compounds:

[0023] Formula II-1: R 2=Me;R 4- =I - ;

[0024] Formula II-2: R 2 =Et; R 4- =I - ;

[0025] Formula II-3: R 2 =i-Pr; R 4- =I - .

[0026] As an example, the compound represented by formula III is any one of the following compounds:

[0027] Formula III-1: R 3 =Me;R 4- =I - .

[0028] In a second aspect, the present invention provides a method for preparing the nitrene compound, comprising the following steps:

[0029] The compound represented by formula IV, formula V or formula VI and R 1 -R 4 、R 2 -R 4 or R 3 -R 4 After addition reaction, a compound represented by Formula I, Formula II, or Formula III is obtained;

[0030] Among them, R 1 、R 2 and R 3 each independently selected from methyl, ethyl, isopropyl or phenyl;

[0031] R 4- selected from iodide, triflate or tetrafluoroborate;

[0032]

[0033] In the above preparation method, the compound represented by formula IV, formula V or formula VI and R 1 -R 4 、R 2 -R 4 or R 3 -R 4 The feeding molar ratio can be 1:5 to 1:10, specifically 1:5;

[0034] The temperature of the addition reaction can be reflux temperature, such as 50° C. to 120° C., and the time can be 5 to 24 hours, specifically 12 hours.

[0035] In a third aspect, the present invention provides the use of the nitrene compound as a photocatalyst for catalyzing the activation of carbon-chlorine bonds. The nitrene compound of the present invention has significant photocatalytic activity.

[0036] In a fourth aspect, the present invention further provides a method for preparing the compound represented by formula VII, comprising the following steps:

[0037] Using the nitrene compound as a photocatalyst, the compound represented by formula VIII and the compound represented by formula IX undergo a free radical addition reaction under blue light irradiation to obtain the compound represented by formula VII;

[0038] R 5 -SeR 6

[0039] Formula VII

[0040]

[0041] Among them, R 5 is selected from substituted or unsubstituted alkyl, cycloalkyl, substituted or unsubstituted carbonyl; R 5 The substituents in the substituted alkyl are selected from alkylcarbonyl, cyano, phenyl, ester, alkylester, alkylamino, carbonyl, phenyl, phenylcarbonyl, Any of R 5 The alkyl group in the substituted alkyl group is selected from C1-C6 alkyl; R 5 The alkyl group in the unsubstituted alkyl group is selected from C1-C12 alkyl; R 5 The substituent in the substituted carbonyl group is selected from phenyl;

[0042] R 6 Selected from substituted or unsubstituted phenyl, thienyl or C1-C6 alkyl (such as methyl); the substituent in the substituted aryl is C1-C6 alkyl, cyano or C1-C6 alkoxy;

[0043] M is Se or S.

[0044] As an example, the compound represented by formula VIII is any one of the compounds represented by formula VIII-1 to formula VIII-17;

[0045]

[0046] As an example, the compound represented by Formula IX is any one of the compounds represented by Formula IX-1 to Formula IX-8;

[0047]

[0048] As an example, the compound represented by formula VII is any one of the compounds represented by formula VII-1 to formula VII-22 below:

[0049]

[0050]

[0051] In the above preparation method, the molar ratio of the compound represented by formula VIII to the compound represented by formula IX can be 2:1 to 1:2, specifically 2:1;

[0052] The free radical addition reaction is carried out under the action of an organic base, wherein the molar ratio of the organic base to the compound represented by formula VIII can be 1:1 to 2:1, specifically 1:1; the organic base is any one of triethylamine, tetramethylethylenediamine (TMEDA) and triethylenediamine (DABCO);

[0053] The molar ratio of the photocatalyst to the compound represented by formula VIII may be 1:10 to 1:20, specifically 1:20;

[0054] The temperature of the free radical addition reaction can be 45 to 55° C., and the time can be 18 to 36 hours, specifically 36 hours.

[0055] In the above preparation method, after the reaction is completed, the step of concentrating the reaction solution and performing column chromatography is further included;

[0056] In the column chromatography, the stationary phase is 200-300 mesh silica gel, and the mobile phase is petroleum ether and ethyl acetate in a volume ratio of 50:1-20:1.

[0057] The nitrene compound of the present invention can be used as an organic photocatalyst to synthesize an organic selenium compound with potential pharmaceutical activity.

[0058] In a fifth aspect, the present invention further provides a method for preparing a compound of formula X, comprising the following steps: using the nitrene compound as a photocatalyst, subjecting the compound of formula XI to a free radical addition reaction with the compound of formula XII under blue light irradiation to obtain a compound of formula X;

[0059]

[0060]

[0061] Among them, R 7 an alkyl group selected from carbomethoxy-substituted alkyl groups;

[0062] • Each independently represents an arbitrary group.

[0063] As an example, the compound represented by formula XI is the compound represented by the following formula XI-1:

[0064]

[0065] Formula XI-1

[0066] As an example, the compound represented by formula XII is any one of the compounds represented by formula XII-1 to formula XII-3 below:

[0067]

[0068] As an example, the compound represented by formula X is any one of the following formulas X-1 to X-3:

[0069]

[0070] In the above preparation method, the molar ratio of the compound represented by formula XI to the compound represented by formula XII can be 2:1 to 1:2, specifically 2:1;

[0071] The free radical addition reaction is carried out under the action of an organic base, wherein the molar ratio of the organic base to the compound represented by formula XI can be 1:1 to 2:1, specifically 1:1; the organic base is any one of triethylamine, TMEDA and DABCO;

[0072] The molar ratio of the photocatalyst to the compound of formula XI may be 1:10 to 1:20, specifically 1:20;

[0073] The temperature of the free radical addition reaction can be 45 to 55° C., and the time can be 18 to 36 hours, specifically 36 hours.

[0074] The present invention has the following beneficial effects:

[0075] The present invention utilizes nitrene compounds as organic photocatalysts to realize free radical addition reactions between alkyl chlorides and organic selenium ether compounds under the action of visible light, thereby highly selectively synthesizing a series of organic selenium compounds with potential pharmaceutical activity. This method provides a simple, efficient, and highly selective synthesis route for organic selenium compounds. The method catalyzes Giese-type (cyclo)addition reactions, Heck-type coupling reactions, and Minisci-type aromatic ring reactions of unsaturated carbon-carbon double bonds. This method does not require the participation of transition metals and utilizes easily available nitrene salts as photocatalysts, thus being novel.

[0076] The invention has the characteristics of readily available raw materials, simple operation, mild reaction conditions, no metal residue, and no involvement of strong acid or strong base. DETAILED DESCRIPTION

[0077] The present invention is further described below with reference to specific examples, but the present invention is not limited to the following examples. The methods described are conventional methods unless otherwise specified. Nuclear magnetic resonance was measured using a Bruker nuclear magnetic resonance instrument.

[0078] The structural formulas of the nitrene catalysts in the following examples are shown in Formulas I to III:

[0079]

[0080] Example 1, Synthesis of Nitrile Catalyst I-1 (R 1 =Me;R 4- =I - )

[0081] 1-Methylbenzotriazole (266.0 mg, 2.0 mmol, 1.0 equiv) represented by Formula IV was dissolved in methyl iodide (10.0 mmol, 5.0 equiv) and heated under reflux for 12 h. After cooling to room temperature, the mixture was filtered and recrystallized from ethanol to obtain the compound.

[0082]

[0083] The structure verification data is as follows:

[0084] 1 H NMR (400MHz, Methanol-d4) δ8.30–8.25(m,2H),8.04–7.94(m,2H),4.65(s,6H).

[0085] 13 C NMR (101MHz, Methanol-d4) δ135.6,131.1,113.5,37.4.

[0086] IR(ATR):2981,1603,1437,1313,1012,774cm -1

[0087] HRMS(ESI):m / z[M] + calcd for C8H 10 N3 + :148.0869; found 148.0866.

[0088] Melting Point: 184-186℃.

[0089] Example 2, Synthesis of Nitrile Catalyst I-2 (R 1 =Et; R 4- =I - )

[0090] 1-Methylbenzotriazole (266.0 mg, 2.0 mmol, 1.0 equiv) represented by Formula IV was dissolved in iodoethane (10.0 mmol, 5.0 equiv) and heated under reflux for 12 h. After cooling to room temperature, the solution was filtered and recrystallized from ethanol.

[0091] The structure verification data is as follows:

[0092] 1 H NMR (500MHz, Methanol-d4) δ8.35–8.31(m,1H),8.29–8.24(m,1H),8.00–7.96(m,2H),5.06(q,J=7.3Hz,2H),4.66(s,3H),1.77(t,J=7.3Hz,3H).

[0093] 13 C NMR (126MHz, Methanol-d4) δ135.7,134.8,131.1,131.0,113.7,113.5,37.6,13.2,13.1.

[0094] IR(ATR):2980,1606,1440,1365,1069,1026,767cm -1

[0095] HRMS(ESI):m / z[M] + calcd for C9H 12 N3 + :162.1026; found 162.1023.

[0096] Melting Point: 145-147℃.

[0097] Example 3, Synthesis of Nitrile Catalyst I-3 (R 1 =i-Pr; R 4- =I - )

[0098] 1-Methylbenzotriazole (266.0 mg, 2.0 mmol, 1.0 equiv) represented by Formula IV was dissolved in 2-iodopropane (10.0 mmol, 5.0 equiv) and heated under reflux for 12 h. After cooling to room temperature, the solution was filtered and recrystallized from ethanol.

[0099] The structure verification data is as follows:

[0100] 1H NMR (500MHz, Methanol-d4) δ8.42–8.33(m,1H),8.31–8.25(m,1H),8.04– 7.95(m,2H), δ5.67–5.59(m,1H),4.66(s,3H),1.82(d,J=6.7Hz,6H).

[0101] 13 C NMR (126MHz, Methanol-d4) δ135.8,134.3,131.1,130.9,113.7,113.6,56.4,37.6,21.0.

[0102] IR(ATR):2978,1439,1235,1139,765,748,628cm -1

[0103] HRMS(ESI):m / z[M] + calcd for C 10 H 14 N3 + :176.1182; found 176.1181.

[0104] Melting Point:205-207℃.

[0105] Example 4, Synthesis of Nitrile Catalyst I-4 (R 1 =Ph; R 4- =I - )

[0106] 1-Methylbenzotriazole (266.0 mg, 2.0 mmol, 1.0 equiv) represented by Formula IV was dissolved in iodobenzene (10.0 mmol, 5.0 equiv) and heated under reflux for 12 h. After cooling to room temperature, the mixture was filtered and recrystallized from ethanol.

[0107] The structure verification data is as follows:

[0108] 1 H NMR (400MHz, Methanol-d4) δ8.30–8.25(m,5H),8.04–7.94(m,4H),4.65(s,3H).

[0109] 13 C NMR (101MHz, Methanol-d4) δ135.6,131.1,130.9,115.7,114.6,113.7,113.6,113.1,37.4.

[0110] IR(ATR):2985,1609,1431,1319,1015,779cm -1

[0111] HRMS(ESI):m / z[M] + calcd for C8H 10 N3 + :196.0869; found 196.0866.

[0112] Melting Point:224-226℃.

[0113] Example 5, Synthesis of Nitrile Catalyst II-1 (R 2 =Me;R 4- =I - )

[0114] 1-Methyl-1H-1,2,3-triazole (163.0 mg, 2.0 mmol, 1.0 equiv) represented by formula V was dissolved in methyl iodide (10.0 mmol, 5.0 equiv) and refluxed for 12 h. After cooling to room temperature, the mixture was filtered and recrystallized from ethanol to obtain the product.

[0115]

[0116] The structure verification data is as follows:

[0117] 1 H NMR (500MHz, Methanol-d4) δ8.74 (s, 2H), 4.38 (s, 6H).

[0118] 13 C NMR (126MHz, Methanol-d4) δ131.5,39.8.

[0119] IR(ATR):3156,1537,1289,1210,1099,750,665cm -1

[0120] HRMS(ESI):m / z[M] + calcd for C4H8N3 + :98.0713; found 98.0716.

[0121] Melting Point:194-196℃.

[0122] Example 6, Synthesis of Nitrile Catalyst II-2 (R 2 =Et; R 4- =I - )

[0123] 1-Methyl-1H-1,2,3-triazole (163.0 mg, 2.0 mmol, 1.0 equiv) represented by formula V was dissolved in iodoethane (10.0 mmol, 5.0 equiv) and heated under reflux for 12 h. After cooling to room temperature, the solution was filtered and recrystallized from ethanol.

[0124] The structure verification data is as follows:

[0125] 1 H NMR (500MHz, Methanol-d4) δ8.79(d,J=1.5Hz,1H),8.71(d,J=1.5Hz,1H),4.71(q,J=7.4Hz,2H),4.38(s,3H),1.64(t,J=7.4Hz,3H).

[0126] 13 C NMR (126MHz, Methanol-d4) δ131.5,130.1,49.3,39.7,13.5.

[0127] IR(ATR):3077,1537,1443,1314,1091,960,808,709cm -1

[0128] HRMS(ESI):m / z[M] + calcd for C5H 10 N3 + :112.0869; found 112.0870.

[0129] Melting Point:159-161℃.

[0130] Example 7, Synthesis of Nitrile Catalyst II-3 (R 2 =i-Pr; R 4- =I - )

[0131] 1-Methyl-1H-1,2,3-triazole (163.0 mg, 2.0 mmol, 1.0 equiv) represented by formula V was dissolved in 2-iodopropane (10.0 mmol, 5.0 equiv) and heated under reflux for 12 h. After cooling to room temperature, the solution was filtered and recrystallized from ethanol.

[0132] The structure verification data is as follows:

[0133] 1H NMR (500MHz, Methanol-d4) δ8.84(d,J=1.5Hz,1H),8.71(d,J=1.5Hz,1H), δ5.17–5.09(m,1H),4.37(s,3H),1.68(d,J=6.7Hz,6H).

[0134] 13 C NMR (126MHz, Methanol-d4) δ131.4,128.8,58.2,39.7,21.2.

[0135] IR(ATR):3057,1537,1279,1213,1099,750cm -1

[0136] HRMS(ESI):m / z[M] + calcd for C6H 12 N3 + :126.1026; found 126.1027.

[0137] Melting Point:205-207℃.

[0138] Example 8, Synthesis of Nitrile Catalyst III-1 (R 3 =Me;R 4- =I - )

[0139] 1-Methyl-1H-naphtho[1,8-de][1,2,3]triazole (400 mg, 2.0 mmol, 1.0 equiv) of formula VI was dissolved in methyl iodide (10.0 mmol, 5.0 equiv) and heated under reflux for 12 h. After cooling to room temperature, the solution was filtered and recrystallized from ethanol.

[0140]

[0141] The structure verification data is as follows:

[0142] 1 H NMR (500MHz, Methanol-d4) δ7.67(dd,J=8.5,0.7Hz,2H),7.5(dd,J=8.6,7.7Hz,2H),7.10(dd,J=7.7,0.7Hz,2H),3.94(s,6H).

[0143] 13 C NMR (126MHz, Methanol-d4) δ133.9,131.3,128.9,126.1,122.3,107.9,43.5.

[0144] IR(ATR):3472,1639,1599,1527,1459,1391,984,819,698cm -1

[0145] HRMS(ESI):m / z[M] + calcd for C 12 H 12 N3 + :198.1026; found 198.1023.

[0146] Melting Point:201-203℃.

[0147] Example 9, Synthesis of Nitrile Catalyst I-5 (R 1 =Me;R 4 =OTf - )

[0148] 1-Methylbenzotriazole (163.0 mg, 2.0 mmol, 1.0 equiv) was dissolved in methyl trifluoromethanesulfonate (10.0 mmol, 5.0 equiv) and heated under reflux for 12 h. After cooling to room temperature, the mixture was filtered and recrystallized from ethanol.

[0149] The structure verification data is as follows:

[0150] 1 H NMR (400MHz, Methanol-d4) δ8.24–8.18(m,2H),7.99–7.93(m,2H),4.61(s,6H).

[0151] 13 C NMR (101MHz, Methanol-d4) δ135.5, 131.0, 120.5 (q, J = 323.2Hz), 113.3, 36.9.

[0152] 19 F NMR(471MHz,Methanol-d4)δ-79.99.

[0153] IR(ATR):2988,1439,1323,1265,1023,775cm -1

[0154] HRMS(ESI):m / z[M] + calcd for C8H 10 N3 + :148.0869; found 148.0867.

[0155] Melting Point: 125-127℃.

[0156] Example 10, Synthesis of Nitrile Catalyst I-6 (R 1 =Me;R 4 =BF4 - )

[0157] 1-Methylbenzotriazole (163.0 mg, 2.0 mmol, 1.0 equiv) was dissolved in methyl tetrafluoroborate (10.0 mmol, 5.0 equiv) and heated under reflux for 12 h. After cooling to room temperature, the mixture was filtered and recrystallized from ethanol.

[0158] The structure verification data is as follows:

[0159] 1 H NMR (400MHz, Methanol-d4) δ8.24–8.18(m,2H),7.99–7.93(m,2H),4.61(s,6H).

[0160] 13 C NMR (101MHz, Methanol-d4) δ135.5, 131.0, 120.5 (q, J = 323.2Hz), 113.3, 36.9.

[0161] 19 F NMR(471MHz,Methanol-d4)δ-79.99.

[0162] IR(ATR):2988,1439,1323,1265,1023,775cm -1

[0163] HRMS(ESI):m / z[M] + calcd for C8H 10 N3 + :148.0869; found 148.0867.

[0164] Melting Point: 125-127℃.

[0165] Example 11: Synthesis of the compound shown in VII-1

[0166] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I -)(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-1 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain a light yellow oil (40mg, 0.164mmol, 82%) of the compound represented by VII-1.

[0167] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-2 (R 1 =Et; R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-1 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-1 as a light yellow oil (20 mg, 0.082mmol, 41%).

[0168] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-3 (R 1 =i-Pr; R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-1 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-1 as a light yellow oil (18.1mg, 0.074mmol, 37%).

[0169] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-4 (R) prepared in Example 4 was added under nitrogen protection. 1 =Ph; R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-1 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-1 as a light yellow oil (19.5mg, 0.040mmol, 40%).

[0170] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst II-1 (R 2 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-1 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-1 as a light yellow oil (39.0mg, 0.160mmol, 80%).

[0171] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst II-2 (R 2 =Et; R 4- =I -)(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-1 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-1 as a light yellow oil (16.1mg, 0.066mmol, 33%).

[0172] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst II-3 (R 2 =i-Pr; R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-1 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-1 as a light yellow oil (14.6mg, 0.060mmol, 30%).

[0173] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst III-1 (R 3 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-1 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-1 as a light yellow oil (24.4mg, 0.100mmol, 50%).

[0174]

[0175]

[0176] The experimental data of VII-1 are as follows:

[0177] 1 H NMR (400MHz, CDCl3) δ7.59–7.57(m,2H),7.34–7.24(m,3H),3.77(q,J=7.2Hz,1H),3.63(s,3H),1.53(d,J=7.2Hz,3H).

[0178] 13 C NMR (101MHz, CDCl3) δ174.0,136.0,129.1,128.7,127.7,52.3,37.2,17.8.

[0179] Example 12: Synthesis of the compound shown in VII-2

[0180] The pre-dried reaction tube was cooled to room temperature under vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-2 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-2.

[0181]

[0182] The experimental data of VII-2 are as follows:

[0183] Colorless oil (36.9 mg, 0.144 mmol, 72%).

[0184] 1 H NMR (500MHz, CDCl3) δ7.57–7.55(m,2H),7.30–7.26(m,3H),3.88(s,2H),1.19(s,9H).

[0185] 13C NMR (126MHz, CDCl3) δ210.8,133.6,129.5,129.2,127.7,44.3,32.7,26.8.

[0186] Example 13: Synthesis of the compound shown in VII-3

[0187] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-3 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-3.

[0188]

[0189] The experimental data of VII-3 are as follows:

[0190] Colorless oil (36.9 mg, 0.144 mmol, 72%).

[0191] 1 H NMR (500MHz, CDCl3) δ7.76–7.70(m,2H),7.46–7.35(m,3H),3.71(q,J=7.4Hz,1H),1.66(d,J=7.3Hz,3H).

[0192] 13 C NMR (126MHz, CDCl3) δ136.5,129.7,129.5,125.8,120.8,19.5,19.2.

[0193] Example 14: Synthesis of the compound represented by formula VII-4

[0194] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I -)(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-4 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-4.

[0195]

[0196] The experimental data of VII-4 are as follows:

[0197] Colorless oil (33.7 mg, 0.136 mmol, 68%).

[0198] 1 H NMR (500MHz, CDCl3) δ7.48–7.42(m,2H),7.26–7.19(m,8H),4.11(s,2H).

[0199] 13 C NMR (126MHz, CDCl3) δ138.6,133.5,130.4,129.0,128.8,128.4,127.3,126.9,32.2.

[0200] Example 15: Synthesis of the compound represented by formula VII-5

[0201] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-5 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate with a volume ratio of 100:1) to obtain the compound represented by formula VII-5.

[0202]

[0203] The experimental data of VII-5 are as follows:

[0204] Colorless oil (30.9 mg, 0.112 mmol, 56%).

[0205] 1 H NMR (500MHz, CDCl3) δ7.49–7.44(m,2H),7.29–7.26(m,2H),7.25–7.13(m, 6H),2.93–2.88(m,2H),2.76–2.70(m,2H),2.02(p,J=7.4Hz,2H).

[0206] 13 C NMR (126MHz, CDCl3) δ141.3,132.5,130.2,129.0,128.5,128.4,126.7,125.9,35.7, 31.6,27.1.

[0207] Example 16: Synthesis of the compound represented by formula VII-6

[0208] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-6 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate with a volume ratio of 100:1) to obtain the compound represented by formula VII-6.

[0209]

[0210] The experimental data of VII-6 are as follows:

[0211] Colorless oil (42.4 mg, 0.130 mmol, 65%).

[0212] 1 H NMR (500MHz, CDCl3) δ7.51–7.44(m,2H),7.26–7.20(m,3H),2.93–2.89(m,2H),1.70(p,J=7.5Hz,2H),1.38–1.23(m,18H),0.88(t,J=6.9Hz,3H).

[0213] 13 C NMR (126MHz, CDCl3) δ132.3,130.7,129.0,126.6,31.9,30.1,29.8,29.6,29.6,29.6, 29.5,29.4,29.1,27.9,22.7,14.1.

[0214] Example 17: Synthesis of the compound represented by formula VII-7

[0215] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-7 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate with a volume ratio of 100:1) to obtain the compound represented by formula VII-7.

[0216]

[0217]

[0218] The experimental data of VII-7 are as follows:

[0219] Colorless oil (26.9 mg, 0.118 mmol, 59%).

[0220] 1 H NMR (500MHz, CDCl3) δ7.51–7.45(m,2H),7.26–7.20(m,3H),2.94–2.90(m,2H),1.73–1.64(m,1H),1.62–1.56(m,2H),0.90(d,J=6.6Hz,6H).

[0221] 13 C NMR (101MHz, CDCl3) δ132.4,130.8,129.1,126.7,39.2,28.5,26.0,22.2.

[0222] Example 18: Synthesis of the compound represented by formula VII-8

[0223] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-8 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate with a volume ratio of 100:1) to obtain the compound represented by formula VII-8.

[0224]

[0225] The experimental data of VII-8 are as follows:

[0226] Colorless oil (22.8 mg, 0.10 mmol, 50%).

[0227] 1 H NMR (500MHz, CDCl3) δ7.50–7.44(m,2H),7.25–7.19(m,3H),2.92–2.88(m,2H),1.70(p,J=7.3Hz,2H),1.41–1.26(m,4H),0.87(t,J=7.2Hz,3H).

[0228] 13 C NMR (126MHz, CDCl3) δ132.3,130.7,129.0,126.6,32.01,29.8,27.9,22.2,14.0.

[0229] Example 19: Synthesis of the compound represented by formula VII-9

[0230] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I -)(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-9 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-9.

[0231]

[0232]

[0233] The experimental data of VII-9 are as follows:

[0234] Colorless oil (34.0 mg, 0.14 mmol, 70%).

[0235] 1 H NMR (400MHz, CDCl3) δ7.53–7.47(m,2H),7.26–7.20(m,3H),2.96–2.90(m,2H),2.39–2.32(m,2H),2.20(s,6H),1.86(p,J=7.2Hz,2H).

[0236] 13 C NMR (101MHz, CDCl3) δ132.6,130.4,129.0,126.7,59.4,45.5,28.1,25.6.

[0237] Example 20: Synthesis of the compound represented by formula VII-10

[0238] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-10 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 20:1) to obtain the compound represented by VII-10.

[0239]

[0240] The experimental data of VII-10 are as follows:

[0241] Colorless oil (28.8 mg, 0.128 mmol, 64%).

[0242] 1 H NMR (500MHz, CDCl3) δ7.53–7.48(m,2H),7.31–7.25(m,3H),2.99(t,J=7.0Hz,2H),2.50(t,J=7.1Hz,2H),1.99(p,J=7.1Hz,2H).

[0243] 13 C NMR (126MHz, CDCl3) δ133.4,129.4,128.8,127.6,119.2,26.1,25.8,17.1.

[0244] Example 21: Synthesis of the compound represented by formula VII-11

[0245] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-11 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-11.

[0246]

[0247]

[0248] The experimental data of VII-11 are as follows:

[0249] Colorless oil (18.1 mg, 0.08 mmol, 40%).

[0250] 1H NMR (500MHz, CDCl3) δ7.55–7.49(m,2H),7.27–7.20(m,3H),3.65-3.60(m,1H),2.13–1.98(m,2H),1.82–1.63(m,4H),1.61-1.55(m,2H).

[0251] 13 C NMR (126MHz, CDCl3) δ133.6,131.2,129.0,127.0,41.9,34.2,25.0

[0252] Example 22: Synthesis of the compound represented by formula VII-12

[0253] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-12 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-2 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 2000 mesh silica gel; mobile phase: petroleum ether and ethyl acetate with a volume ratio of 100:1) to obtain the compound represented by VII-12.

[0254]

[0255] The experimental data of VII-12 are as follows:

[0256] Colorless oil (44.4 mg, 0.172 mmol, 86%).

[0257] 1 H NMR (500MHz, CDCl3) δ7.44–7.36(m,2H),7.22–7.12(m,2H),3.77(q,J=7.1Hz,1H),3.65(s,3H),2.34(s,3H),1.55(d,J=7.1Hz,3H).

[0258] 13 C NMR (126MHz, CDCl3) δ174.0,138.8,136.4,132.7,129.4,128.8,127.5,52.1,37.2, 21.3,17.8.

[0259] IR(ATR):2918,1729,1433,1330,1255,1059,995,853cm -1

[0260] HRMS(ESI):m / z[M+Na] + calcd for C 11 H 14 O2SeNa + :281.0051; found 281.0049.

[0261] Example 23: Synthesis of the compound represented by formula VII-13

[0262] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-12 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-3 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-13.

[0263]

[0264] The experimental data of VII-13 are as follows:

[0265] Colorless oil (42.7 mg, 0.156 mmol, 78%).

[0266] 1 H NMR (500MHz, CDCl3) δ7.25–7.12(m,3H),6.89–6.87(m,1H),3.82–3.77(m,4H),3.67(s,3H),1.56(d,J=7.2Hz,3H).

[0267] 13 C NMR (126MHz, CDCl3) δ174.0,159.6,129.8,128.6,127.7,120.6,114.5,55.3,52.2, 37.3,17.8.

[0268] IR(ATR):2950,1727,1586,1475,1330,1210,1035,992,838cm -1

[0269] HRMS(ESI):m / z[M+Na] + calcd for C 11 H 14 O3SeNa + :297.0000; found 296.9997.

[0270] Example 24: Synthesis of the compound represented by formula VII-14

[0271] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-12 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-4 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate with a volume ratio of 50:1) to obtain the compound represented by VII-14.

[0272]

[0273] The experimental data of VII-14 are as follows:

[0274] Colorless oil (40.9 mg, 0.152 mmol, 76%).

[0275] 1 H NMR (500MHz, CDCl3) δ7.69–7.64(m,2H),7.58–7.55(m,2H),3.90(q,J=7.2Hz,1H),3.69(s,3H),1.61(d,J=7.2Hz,3H).

[0276] 13 C NMR (126MHz, CDCl3) δ173.4,135.6,134.2,133.2,133.0,132.3,118.5,111.5,52.5, 37.3,17.7.

[0277] IR(ATR):2226,1726,1586,1486,1330,1258,1061,821cm -1

[0278] HRMS(ESI):m / z[M+Na] + calcd for C 11 H 11 O2NSeNa + :291.9847; found 291.9846.

[0279] Example 25: Synthesis of the compound represented by formula VII-15

[0280] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-12 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-5 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200-300 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-15.

[0281]

[0282] The experimental data of VII-15 are as follows:

[0283] Colorless oil (38.2 mg, 0.142 mmol, 71%).

[0284] 1 H NMR (500MHz, CDCl3) δ7.52(d,J=8.4Hz,2H),7.32(d,J=8.4Hz,2H),3.75(q,J=7.1Hz,1H),3.65(s,3H),1.53(d,J=7.1Hz,3H),1.31(s,9H).

[0285] 13 C NMR (126MHz, CDCl3) δ174.1,152.0,135.9,126.2,124.2,52.2,37.2,34.8,31.3, 17.9.

[0286] IR(ATR):2959,1730,1449,1330,1206,1143,824cm -1

[0287] HRMS(ESI):m / z[M+Na] + calcd for C 14 H 20 O2SeNa + :323.0521; found 323.0518.

[0288] Example 26: Synthesis of the compound represented by formula VII-16

[0289] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-12 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-6 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-16.

[0290]

[0291] The experimental data of VII-16 are as follows:

[0292] Colorless oil (40.0 mg, 0.160 mmol, 80%).

[0293] 1 H NMR (500MHz, CDCl3) δ7.46(dd,J=5.3,1.2Hz,1H),7.24(dd,J=3.5,1.2Hz,1H), 7.03(dd,J=5.3,3.5Hz,1H),3.70–3.66(m,4H),1.53(d,J=7.1Hz,3H).

[0294] 13C NMR (126MHz, CDCl3) δ173.4,138.3,132.8,128.3,120.9,52.3,39.2,17.4. IR(ATR):2917,2848,1728,1644,1433,1329,962,845cm -1

[0295] HRMS(ESI):m / z[M+Na] + calcd for C8H 10 O2SSeNa + :272.9459; found 272.9456.

[0296] Example 27: Synthesis of the compound represented by formula VII-17

[0297] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-13 (0.4mmol, 2.0equiv), organic selenide ether represented by formula IX-7 (0.2mmol, 1.0equiv), 1.0 ml of anhydrous acetonitrile was added under nitrogen protection, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 20:1) to obtain the compound represented by VII-17.

[0298]

[0299] The experimental data of VII-17 are as follows:

[0300] Colorless oil (31.7 mg, 0.148 mmol, 74%).

[0301] 1 H NMR (500MHz, CDCl3) δ7.96–7.93(m,2H),7.58–7.53(m,1H),7.48–7.44(m,2H),3.75(s,2H),2.07(s,3H).

[0302] 13 C NMR (126MHz, CDCl3) δ194.5,135.1,133.2,128.7,128.6,27.9,5.9.

[0303] Example 28: Synthesis of the compound represented by formula VII-18

[0304] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-12 (0.4mmol, 2.0equiv), organic thioether represented by formula IX-8 (0.2mmol, 1.0equiv), 1.0 ml of anhydrous acetonitrile was added under nitrogen protection, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate with a volume ratio of 50:1) to obtain the compound represented by VII-18.

[0305]

[0306] The experimental data of VII-18 are as follows:

[0307] Colorless oil (22.4 mg, 0.114 mmol, 57%).

[0308] 1 H NMR (500MHz, CDCl3) δ7.47–7.43(m,2H),7.34–7.28(m,3H),3.80(q,J=7.1Hz,1H),3.67(s,3H),1.49(d,J=7.1Hz,3H).

[0309] 13 C NMR (126MHz, CDCl3) δ173.1,133.1,133.0,129.0,128.1,52.3,45.2,17.5.

[0310] Example 29: Synthesis of the compound represented by formula VII-19

[0311] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I -)(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-14 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-19.

[0312]

[0313] The experimental data of VII-19 are as follows:

[0314] Colorless oil (53.6 mg, 0.108 mmol, 54%).

[0315] 1 H NMR (400MHz, CDCl3) δ8.19 (dd, J=8.0, 1.6Hz, 1H), 7.62–7.54 (m, 2H), 7.47–

[0316] 7.27(m,5H),7.24–7.10(m,4H),4.34(s,2H),4.18–4.09(m,2H),3.69(q,J=7.2Hz, 1H),2.80(t,J=7.2Hz,2H),2.00–1.88(m,2H),1.46(d,J=7.2Hz,3H).

[0317] 13 C NMR (101MHz, CDCl3) δ191.4,173.9,142.8,140.3,138.0,136.2,133.4,132.8,132.6, 131.6,131.6,131.0,129.9,129.2,128.7,127.1,126.9,126.4,64.2,51.1,45.3,29.1,23.8,18.5.

[0318] IR(ATR):2973,1729,1671,1586,1475,1427,1071,731,690cm -1

[0319] HRMS(ESI):m / z[M+Na] + calcd for C 26 H 24 O3SSeNa +:519.0504; found 519.0491.

[0320] Example 30: Synthesis of the compound represented by formula VII-20

[0321] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-15 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-20.

[0322]

[0323] The experimental data of VII-20 are as follows:

[0324] White solid (50.4 mg, 0.098 mmol, 49%).

[0325] 1 H NMR (400MHz, CDCl3) δ8.17(d,J=2.3Hz,1H),8.09–8.07(m,1H),7.55–7.49(m,2H),7.27–7.21(m,3H),7.01(d,J=8.9Hz,1H ),4.38(t,J=6.1Hz,2H),3.90(d,J=6.5Hz,2H),3.02(t,J=7.2Hz,2H),2.74(s,3H),2.24–2.15(m,1H),2.17–2.07(m,2H), 1.09(d,J=6.7Hz,6H).

[0326] 13 C NMR (101MHz, CDCl3) δ167.4,162.6,161.9,161.4,133.0,132.7,132.2,129.8,129.3, 127.2,126.0,121.6,115.5,112.7,103.1,64.6,29.4,28.3,24.1,19.2,17.6.

[0327] IR(ATR):2957,2227,1686,1601,1507,1431,1044,736,691cm -1

[0328] HRMS(ESI):m / z[M+Na] + calcd for C 25 H 26 N2O3SSeNa + :537.0722; found 537.0717.

[0329] Melting Point:97-99℃.

[0330] Example 31: Synthesis of the compound represented by formula VII-21

[0331] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-16 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by VII-21.

[0332]

[0333] The experimental data of VII-21 are as follows:

[0334] Colorless oil (52.2 mg, 0.118 mmol, 59%).

[0335] 1 H NMR(500MHz, CDCl3)δ7.54–7.50(m,2H),7.47–7.33(m,6H),7.24–7.19(m, 3H),7.16–7.07(m,2H),4.18(t,J=6.2Hz,2H),3.73(q,J=7.2Hz,1H),2.84(t,J=7.3Hz,2H),2.03–1.92(m,2H),1.52(d,J=7.2Hz,3H).

[0336] 13 C NMR (126MHz, CDCl3) δ174.0, 159.8 (d, J = 249.7Hz), 142.0 (d, J = 7.7Hz), 135.6, 132.9,131.0(d,J=4.1Hz),129.9,129.2,129.1(d,J=2.9Hz),128.6,128.0(d,J=13.7Hz ),127.8,127.1,123.6(d,J=3.4Hz),115.3(d,J=23.8Hz),64.3,45.1,29.2,23.9,18.4. IR(ATR):2975,1730,1579,1478,1170,1072,873,765cm -1

[0337] HRMS(ESI):m / z[M+Na] + calcd for C 24 H 23 FO2SeNa + :465.0740; found 465.0730.

[0338] Example 32: Synthesis of the compound represented by formula VII-22

[0339] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula VIII-17 (0.4mmol, 2.0equiv), and organic selenide ether represented by formula IX-1 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate with a volume ratio of 50:1) to obtain the compound represented by VII-22.

[0340]

[0341] The experimental data of VII-22 are as follows:

[0342] Pale yellow oil (62.2 mg, 0.112 mmol, 56%).

[0343] 1H NMR(400MHz, CDCl3)δ7.69–7.60(m,2H),7.48–7.38(m,4H),7.24–7.17(m, 3H),6.95(d,J=2.5Hz,1H),6.86(dd,J=9.0,0.5Hz,1H),6.66(dd,J=9.0,2.5Hz,1H), 4.18(t,J=6.2Hz,2H),3.81(s,3H),3.64(s,2H),2.84(t,J=7.3Hz,2H),2.37(s,3H), 2.03–1.94(m,2H).

[0344] 13 C NMR (101MHz, CDCl3) δ170.7,168.3,156.1,139.3,135.9,133.9,132.7,131.2,130.8, 130.6,129.7,129.1,127.0,115.0,112.5,111.7,101.2,64.2,55.7,30.4,29 .1,23.7,13.4.IR(ATR):2929,1731,1678,1589,1475,1355,1087,831,733cm -1

[0345] HRMS(ESI):m / z[M+Na] + calcd for C 28 H 26 ClNO4SeNa + :578.0608; found 578.0602.

[0346] Example 33: Synthesis of the compound represented by formula X-1

[0347] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula XI-1 (0.4mmol, 2.0equiv), organic olefin represented by formula XII-1 (0.2mmol, 1.0equiv), 1.0ml of anhydrous acetonitrile was added under nitrogen protection, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 50:1) to obtain the compound represented by formula X-1.

[0348]

[0349] The experimental data of X-1 are as follows:

[0350] Colorless oil (62.2 mg, 0.112 mmol, 56%).

[0351] (52.3mg, 0.162mmol, 81%, E:Z=4.6:1).

[0352] 1 H NMR (400MHz, CDCl3) δ7.45–7.36(m,3H),7.29–7.17(m,7H),5.53(t,J=7.6Hz,1H),4.49(s,2H),3.63(s,3H),3.21(d,J=7.7Hz,2H),2.28(s,3H).

[0353] 13 C NMR (101MHz, CDCl3) δ171.3,171.0,141.6,137.4,134.2,129.3,129.0,128.9,128.8, 128.4,127.3,123.2,52.1,49.0,33.9,22.5.

[0354] IR(ATR):2915,1735,1644,1493,1386,1169,980,780cm -1

[0355] HRMS(ESI):m / z[M+Na] + calcd for C 20 H 21 NO3Na + :346.1413; found 346.1406.

[0356] Example 34: Synthesis of the compound represented by formula X-2

[0357] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I -)(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula XI-1 (0.4mmol, 2.0equiv), and organic olefin represented by formula XII-2 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 20:1) to obtain the compound represented by formula X-2.

[0358]

[0359] The experimental data of X-2 are as follows:

[0360] White solid (40.4 mg, 0.174 mmol, 87%).

[0361] 1 H NMR (500MHz, CDCl3) δ12.89 (s, 1H), 7.86 (d, J = 8.7Hz, 1H), 7.54–7.51 (m, 1H), 7.39–7.32(m,2H),4.30(q,J=7.2Hz,1H),3.73(s,3H),1.66(d,J=7.2Hz,3H).

[0362] 13 C NMR (126MHz, CDCl3) δ173.3,158.6,156.3,132.8,131.2,130.5,129.3,124.4,116.0, 52.4,43.7,14.5.

[0363] IR(ATR):2839,1731,1660,1561,1432,1085,763cm -1

[0364] HRMS(ESI):m / z[M+Na] + calcd for C 12 H 12 N2O3Na + :255.0740; found 255.0737.

[0365] Melting Point: 184-186℃.

[0366] Example 35: Synthesis of the compound represented by formula X-3

[0367] The reaction tube dried in advance was cooled to room temperature in vacuum, and the nitrene catalyst I-1 (R 1 =Me;R 4- =I - )(0.02mmol, 10mol%), triethylamine (0.4mmol, 2.0equiv), alkyl chloride represented by formula XI-1 (0.4mmol, 2.0equiv), and organic olefin represented by formula XII-3 (0.2mmol, 1.0equiv) were added under nitrogen protection. 1.0 ml of anhydrous acetonitrile was added, and the mixture was moved to 25°C and irradiated with stirring under blue light (blue LED, 100W), generally overnight. The reaction solution was concentrated and separated and purified by column chromatography (stationary phase: 200 mesh silica gel; mobile phase: petroleum ether and ethyl acetate in a volume ratio of 20:1) to obtain the compound represented by formula X-3.

[0368]

[0369] The experimental data of X-3 are as follows:

[0370] Colorless oil (28.8 mg, 0.116 mmol, 58%).

[0371] 1 H NMR (400MHz, CDCl3) δ8.20 (dd, J=5.2, 1.6Hz, 1H), 7.43 (dd, J=7.2, 1.6Hz, 1H), 6.98(dd,J=7.2,5.3Hz,1H),3.55(s,3H),3.31(s,3H),2.31–2.20(m,1H),2.20–2.07(m,2H),2.00–1.88(m,1H),1.41(s,3H).

[0372] 13 C NMR (101MHz, CDCl3) δ179.6,173.1,156.9,147.2,130.4,127.3,118.3,51.8,47.4, 32.5,29.4,25.4,23.2.

[0373] IR(ATR):2925,1714,1592,1467,1345,1133,1020,780cm -1

[0374] HRMS(ESI):m / z[M+Na] + calcd for C 13 H 16 N2O3Na +:271.1053;found 271.1050.

[0375] Melting Point:184-186℃。

Claims

1. A method for preparing a compound represented by formula VII, comprising the following steps: Using the compound represented by Formula I, Formula II or Formula III as a photocatalyst, the compound represented by Formula VIII and the compound represented by Formula IX undergo a free radical addition reaction under blue light irradiation to obtain the compound represented by Formula VII; The free radical addition reaction is carried out under the action of an organic base, which is any one of triethylamine, tetramethylethylenediamine and triethylenediamine; in, R 1 、R 2 and R 3 are each independently selected from methyl, ethyl, isopropyl or phenyl; R 4- selected from iodide, triflate or tetrafluoroborate; The compound represented by formula VIII is any one of the compounds represented by formula VIII-1 to formula VIII-17; ； The compound represented by formula IX is any one of the compounds represented by formula IX-1 to formula IX-8; ； The compound represented by formula VII is any one of the compounds represented by formula VII-1 to formula VII-22 below:

2. The preparation method according to claim 1, wherein: The molar ratio of the compound represented by formula VIII to the compound represented by formula IX is 2:1 to 1:2; The molar ratio of the organic base to the compound represented by formula VIII is 1:1 to 2:1; The molar ratio of the photocatalyst to the compound represented by formula VIII is 1:10 to 1:20; The temperature of the free radical addition reaction is 45-55° C., and the time is 18 h-36 h.

3. The preparation method according to claim 1, wherein: The method for preparing the compound represented by formula I, formula II or formula III comprises the following steps: The compound represented by formula IV, formula V or formula VI and R 1 -R 4 、R 2 -R 4 or R 3 -R 4 After addition reaction, a compound represented by Formula I, Formula II, or Formula III is obtained; Among them, R 1 、R 2 and R 3 each independently selected from methyl, ethyl, isopropyl or phenyl; R 4- selected from iodide, triflate or tetrafluoroborate; 4. The preparation method according to claim 3, wherein: The compound represented by formula IV, formula V or formula VI and R 1 -R 4 、R 2 -R 4 or R 3 -R 4 The feeding molar ratio is 1:5~1:10; The temperature of the addition reaction is reflux temperature, and the time is 5 to 24 hours.

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