CN114643080B - 一种烯烃光二聚催化剂及其制备方法和应用 - Google Patents
一种烯烃光二聚催化剂及其制备方法和应用 Download PDFInfo
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- CN114643080B CN114643080B CN202210274173.7A CN202210274173A CN114643080B CN 114643080 B CN114643080 B CN 114643080B CN 202210274173 A CN202210274173 A CN 202210274173A CN 114643080 B CN114643080 B CN 114643080B
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000011907 photodimerization Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 229940126062 Compound A Drugs 0.000 claims description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
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- 238000000034 method Methods 0.000 claims description 8
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- SILNNFMWIMZVEQ-UHFFFAOYSA-N 1,3-dihydrobenzimidazol-2-one Chemical compound C1=CC=C2NC(O)=NC2=C1 SILNNFMWIMZVEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
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- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 2
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 abstract description 5
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- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical group C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 abstract description 2
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
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- QKHRGPYNTXRMSL-VOTSOKGWSA-N 4-[(e)-2-phenylethenyl]pyridine Chemical class C=1C=CC=CC=1/C=C/C1=CC=NC=C1 QKHRGPYNTXRMSL-VOTSOKGWSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KSCRVOKQPYZBHZ-IXPOFIJOSA-N benzyl n-[(2s)-1-[[(2s)-1-[[(2s)-1-(1,3-benzothiazol-2-yl)-1-oxo-3-[(3s)-2-oxopyrrolidin-3-yl]propan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-methyl-1-oxobutan-2-yl]carbamate Chemical compound N([C@H](C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C[C@H]1C(NCC1)=O)C(=O)C=1SC2=CC=CC=C2N=1)C(C)C)C(=O)OCC1=CC=CC=C1 KSCRVOKQPYZBHZ-IXPOFIJOSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract
本发明公开了结构式（E）所示的烯烃光二聚催化剂。本发明烯烃光二聚催化剂中引入苯并咪唑酮单元增加了空间位阻，从而抑制了金属卡宾模板的二聚反应，使得该模板可以在均相溶液中重复参与烯烃的[2+2]光化学反应，实现了烯烃[2+2]光化学的催化反应。该催化剂具有易合成，催化反应操作简单，对设备的要求低，底物普适性好，得到的环丁烷衍生物立体选择性好，产物易于分离，收率高等特点。
Description
技术领域
本发明涉及一种烯烃光二聚催化剂及其制备方法和应用，属于合成化学领域。
背景技术
环加成反应是经典有机反应，烯烃的[4+2]环加成在加热条件下就可以顺利地进行，如Diels Alder反应，而[2+2]环加成反应则需要在光照、路易斯酸或者过渡金属作用下才能进行。
光化学[2+2]反应指在加热或者光照条件下，分子内或者分子间的两个不饱和键，如碳碳双键，碳碳叁键，碳氧双键等发生加成反应生成四元环的过程。其中烯烃在光照作用下的[2+2]环加成反应发展较早，已广泛地应用到有机合成中，是人们得到四元环类化合物最直接有效的方法。在[2+2]光环加成反应中，烯烃分子在紫外光的激发下进入激发态，其HOMO轨道与另一个烯烃分子的LUMO轨道正面靠近，从而发生[2+2]环加成反应。
1918年，Kohlschütter教授提出了局部化学原理，这一规则指出，在固态下化合物中的分子或是原子会以最小量发生反应。1971年, Schmidt教授在之前的研究基础上在Pure Appl. Chem.杂志提出了著名的拓扑化学规则，即Schmidt规则，该规则指出，在晶态下，发生[2+2]光环加成反应需满足两个条件：1、两个碳碳双键之间的距离需要在3.5-4.2Å之间；2、反应物需处在合适的空间位置使得C=C按平行方式排列。该规则的提出推动了[2+2]光环加成反应的蓬勃发展。目前，主客体效应、分子间的弱作用力以及金属配位等导向作用成功实现了环丁烷衍生物的制备。然而，由于溶液中的溶剂效应的影响，以上大多数策略只能在固态下实现，这使得环丁烷衍生物大量制备受到了限制。
发明内容
本发明的目的是针对现有技术中的不足，提供一种烯烃光二聚催化剂的制备方法及其应用，通过金卡宾的模板效应，可在温和条件下实现均相溶液中的环丁烷衍生物的催化合成。
为实现上述目的，本发明公开了如下技术方案：
结构式（E）所示的烯烃光二聚催化剂，
OTf 为CF3SO3。
上述结构式（E）所示的烯烃光二聚催化剂的制备方法，包括以下步骤：
（1）将2-羟基苯并咪唑与甲醛水溶液混合加热，重结晶后将固体分散在二氯甲烷中，加入二氯亚砜，蒸干溶剂得化合物A；
（2）向化合物A中加入碳酸钾和咪唑，在乙腈中加热反应，抽滤得到化合物B；
（3）化合物A和化合物B于85~90℃在乙腈中加热，得到的沉淀化合物与NH4PF6在水-甲醇混合溶剂中进行离子交换，得咪唑鎓环蕃化合物C；
（4）将咪唑鎓环蕃化合物C与四氢噻吩氯化亚金在乙酸钠存在下在DMSO中反应，反应结束后加入甲醇析出化合物D；
（5）化合物D在DMF中与吡啶、三氟甲磺酸银反应得到催化剂E；
上述步骤（5）中，用醚洗涤产物，所述醚是异丙醚、甲基叔丁基醚或乙醚，优选为乙醚。
上述结构式（E）所示的化合物作为催化剂在[2+2]光化学环加成反应中的应用，
或者
本发明的优点：本发明苯并咪唑酮单元的引入增加了空间位阻，从而抑制了金属卡宾模板的二聚反应，使得该模板可以在均相溶液中重复参与烯烃的[2+2]光化学反应，实现了烯烃[2+2]光化学的催化反应。金属卡宾模板由于其较强的结合能力使得模板在均相溶液中也可以高效进行模板反应，催化量模板的加入大大降低了反应成本，该催化剂具有易合成，催化反应操作简单，对设备的要求低，底物普适性好，得到的环丁烷衍生物立体选择性好（均为rctt构型），产物易于分离，收率高等特点。同时实现了4-苯乙烯吡啶衍生物的单齿配体的[2+2]光化学的催化反应，为环丁烷衍生物的大量制备提供了新的思路。本发明利用溶液中的配体交换原理，合成的模板催化剂中的吡啶分子可被烯烃配体所替代，在365nm紫外光照射下进行[2+2]光化学环加成反应，由于生成的环丁烷的环张力导致了与模板的解离，游离的烯烃配体会重新配位，进而实现了环丁烷衍生物的催化合成。
说明书附图
图1. 烯烃光二聚催化剂E的1H NMR 核磁谱图；
图2. 烯烃光二聚催化剂E的13C NMR 核磁谱图；
图3. 烯烃光二聚催化剂E的高分辨质谱图；
图4. 环丁烷衍生物2a的1H NMR 核磁谱图；
图5. La配体的光催化反应的原位核磁监测图 a) La配体在相当于La物质的量的20 mol% 烯烃光二聚模板催化剂E存在下的核磁共振氢谱 (400 MHz，298 K，DMSO-d 6) (b)光照5 min; (c) 光照10 min; (d) 光照15 min; (e) 光照20 min; (f) 光照25 min;(g) 光照60 min; (h) 加入乙酸钠；
图6. 环丁烷衍生物2i的1H NMR 核磁谱图。
具体实施方式
下面通过实施例进一步具体描述本发明，本发明并不局限于下述实施例。
实施例1：化合物A的制备
将2-羟基苯并咪唑(10.0 g, 74.63 mmol)、水(60 mL)以及37%甲醛水溶液(20mL)依次加入250 mL圆底烧瓶中，加热回流30分钟。反应结束后，蒸干溶剂，粗品用水重结晶得到白色固体14.0 g，产率97%。1H NMR (DMSO-d 6, 400 MHz) δ = 7.25-7.23 (m, 2H, Ar-H), 7.10-7.07 (m, 2H, Ar-H), 6.42-6.39 (t, 2H, O-H, J = 7.2 Hz), 5.23-5.22(d, 4H, C-H, J = 7.2 Hz) ppm。
将化合物a(5.0 g, 25.75 mmol)以及二氯甲烷(100 mL)加入250 mL圆底烧瓶中，在0摄氏度下，缓慢滴入二氯亚砜(7.5 mL, 103.3 mmol)，滴加完毕后室温搅拌24小时。减压蒸去溶剂得到目标化合物A，白色固体，5.5 g，产率92%。1H NMR (DMSO-d 6, 400 MHz) δ =7.49-7.46 (m, 2H, Ar-H), 7.27-7.25 (m, 2H, Ar-H), 6.02 (s, 4H, C-H) ppm。
实施例2：化合物B的制备
将化合物A(6.0 g, 25.97 mmol)咪唑(8.8 g, 129.41 mmol)、碳酸钾(10.8 g,78.14 mmol)、以及乙腈(100 mL)加入250 mL圆底烧瓶中，在90摄氏度下加热8小时。反应结束后，蒸干溶剂后用水洗涤、干燥得到目标化合物B，白色固体，4.9 g，产率64%。1H NMR(DMSO-d 6, 400 MHz) δ = 7.93 (s, 2H, C-H), 7.59-7.56 (m, 2H, Ar-H), 7.28 (s,2H, C-H), 7.17-7.14 (m, 2H, Ar-H), 6.89 (s, 2H, C-H), 6.12 (s, 4H, C-H) ppm。13C NMR (DMSO-d 6, 100 MHz) δ = 153.0, 137.7, 129.2, 127.5, 122.5, 119.2,109.0, 50.4. HRMS (ESI, positive ions): m/z = 295.1480 (calcd for [B+ H]+295.1302)。
实施例3：化合物C的制备
将化合物A(3.6 g, 15.58 mmol)、化合物B(4.5 g, 15.29 mmol)以及乙腈(50mL)依次加入250 mL圆底烧瓶中，在85摄氏度条件下加热5小时，加热过程中逐渐出现白色固体。反应结束后，抽滤，真空干燥，得到白色固体，将得到的白色固体转移至250 mL圆底烧瓶中，加入100 mL水和50 mL甲醇，并在该悬浮液中加入NH4PF6 (6.0 g, 36.81 mmol)，室温搅拌过夜。反应结束后过滤，滤饼用50 mL 乙腈洗涤，过滤，接着将得到的滤饼转移至250mL圆底烧瓶中，加入30 mL水和90 mL甲醇，并在该悬浮液中加入NH4PF6 (12.0 g, 73.62mmol)，在室温搅拌半小时后，加热至100摄氏度，反应12小时，过滤，将过滤后的白色固体分别用甲醇和水溶液洗涤，洗涤后固体进行真空干燥，即为目标化合物C，4.9 g (43%, 6.59mmol)。1H NMR (DMSO-d 6, 400 MHz) δ = 9.47 (s, 2H, C-H), 7.89 (s, 4H, C-H), 7.68(s, 4H, Ar-H), 7.17 (s, 4H, Ar-H), 6.45 (s, 8H, C-H)。13C NMR (DMSO-d 6, 100MHz) δ = 153.8, 139.4, 127.7, 122.8, 122.1, 109.2, 52.3 ppm. HRMS (ESI,positive ions): m/z = 599.1547 (calcd for [C-PF6]+ 599.1502)。
实施例4：化合物D的制备
将化合物C (100.0 mg, 0.14 mmol)，四氢噻吩氯化亚金(110.0 mg, 0.34 mmol)以及乙酸钠(55.0 mg, 0.67 mmol)分散在5 mL 二甲基亚砜中，在室温下搅拌24小时，离心，清液用50 mL甲醇逼出固体，过滤，将过滤后的白色固体分别用甲醇和水溶液洗涤，洗涤后固体进行真空干燥，即为目标化合物D，105.1 mg (0.08 mmol, 85%)。 1H NMR (DMSO-d 6,400 MHz) δ = 7.72-7.69 (m, 4H, Hb), 7.13 (s, 4H, He), 7.06-7.04 (m, 4H, Ha),6.20 (d, 4H, Hd, J = 14.4 Hz), 6.00 (d, 4H, Hd, J = 14.4 Hz)。13C NMR (DMSO-d 6,100 MHz) δ = 169.9 (Cg), 152.4 (Cf), 127.4 (Cc), 122.3 (Cb), 121.9 (Ce), 110.8(Ca), 55.0 (Cd) ppm. HRMS (ESI, positive ions): m/z = 811.0985 (calcd for [D-Cl]+ 811.0723)。
实施例5：催化剂E的制备
将化合物D (50.0 mg, 0.06 mmol) 分散在3 mL DMF中，加入吡啶 (50 uL, 0.62mmol)，向该体系中缓慢滴入溶解有三氟甲磺酸银 (35 mg, 0.14 mmol) 的2 mL DMF溶液，滴完后室温搅拌1小时，离心，清液用乙醚逼出固体，过滤的白色粉末，用乙醚洗涤，真空干燥后即为目标化合物E，45.3 mg (0.03 mmol, 62%)。
图1为本发明实施例5中化合物E的核磁氢谱表征，从图1可以得出化合物E的结构与核磁氢谱信息吻合，从图上可以看到咪唑环蕃骨架上的亚甲基裂分成了两组峰，这说明形成了化合物E之后，环蕃骨架的旋转受到了抑制，使得亚甲基上的两个氢的化学环境变的不同，由于同碳耦合的作用，裂分为两组氢。其具体谱图信息为：1H NMR (DMSO-d 6, 400MHz) δ = 8.14 (br, 4H, Hh), 8.06 (t, 2H, Hj, J = 8.0 Hz), 7.81 (br, 4H, Hb),7.56 (br, 4H, He), 7.48 (br, 4H, Hi), 7.01 (br, 4H, Ha), 6.56 (d, 4H, Hd, J =13.6 Hz), 6.13 (d, 4H, Hd, J = 13.6 Hz)。
图2为本发明实施例5中化合物E的核磁碳谱表征，从图2可以得出化合物E的结构与核磁碳谱信息吻合，其具体谱图信息为：13C NMR (DMSO-d 6, 100 MHz) δ = 151.3 (Ch),150.9 (Cf), 141.4 (Cj), 126.4 (Cc), 122.3 (Ci), 122.1 (Ca), 119.1 (Ce), 110.0(Cb), 55.1 (Cd) ppm。
图3为本发明实施例5中化合物E的高分辨质谱表征，从图3可以得出化合物E的二价阳离子峰可以被高分辨质谱检测到，且峰形吻合，其具体谱图信息为：电喷雾电离质谱(正离子模式): m/z = 502.0939 (该二价阳离子 [E-2OTf]2+ 的理论模拟质荷比值为502.0937)。结合图1-3的谱图表征，说明已成功制备化合物E，其结构为目标结构。
实施例6烯烃分子La的光化学催化反应
将催化剂E (0.01 mmol，13 mg)，烯烃配体 La (0.1 mmol，18.2 mg) 溶解于5 mL二甲基亚砜中，置于365 nm的氙灯光源下光照5小时，待反应结束后，将反应液倒入水中，用二氯甲烷萃取，浓缩有机相后用二氯甲烷/甲醇柱层析得到产物15.3 mg，收率84%。
图4为本发明实施例6中化合物2a的核磁氢谱表征, 其谱图信息为1H NMR (DMSO-d 6, 400 MHz) δ = 8.34 (d, 8H, Ar-H, J = 4.8 Hz), 7.22 (d, 8H, Ar-H, J = 4.8Hz), 4.66 (s, 4H, C-H). 该化合物与文献中已经报道rctt构型的核磁谱图信息一致。
实施例7烯烃分子La的光化学催化反应过程检测
将催化剂E (0.002 mmol，2.6 mg)，烯烃配体 La (0.01 mmol，1.8 mg) 溶解于0.5 mL 氘代二甲基亚砜中，置于365 nm的氙灯光源下光照，间隔5分钟对其进行核磁测试。
图5为本发明实施例7烯烃配体La的光化学环加成催化反应的原位的核磁监测图，从图上可以看到，该反应的反应速率随着时间的增加而逐渐减缓，到25分钟时反应已经达到平衡状态，随着后续反应时间的延长，体系中的各个组份不再有明显的变化，并且，如图5h所示，在加入乙酸钠之后，从核磁谱图上可以观测到与模板配位的环丁烷衍生物发生解离。
实施例8使用催化剂E进行烯烃配体Li的光化学反应
将催化剂E (0.002 mmol，2.6 mg)，烯烃配体 Li (0.1 mmol，18.1 mg) 溶解于1.5 mL 二甲基亚砜中，置于365 nm的氙灯光源下光照5小时，待反应结束后，将反应液倒入水中，用二氯甲烷萃取，浓缩有机相后用二氯甲烷/甲醇柱层析得到产物11.2 mg，收率62%。
图6为本发明实施例8中化合物2i的核磁氢谱表征, 其谱图信息为1H NMR (CDCl3,400 MHz) δ = 8.39 (m, 8H, Ar-H), 7.10 (m, 14H, Ar-H), 4.47 (d, 4H, C-H, J =2.8 Hz), 4.46 (d, 12H, C-H, J = 2.8 Hz). 该化合物与文献中已经报道的rctt构型核磁谱图信息一致。
实施例9本发明涉及的光催化反应烯烃配体以及环丁烷产物可以有多种选择，以下表格中是部分实例。
以上所述仅是本发明的优选实施方式，应当指出，对于本领域的普通技术人员,在不脱离本发明的前提下，还可以对本发明做出的若干改进和补充，这些改进和补充，也应视为本发明的保护范围。
Claims (5)
1.结构式（E）所示的烯烃光二聚催化剂，
OTf 为CF3SO3。
2.权利要求1所述催化剂的制备方法，其特征在于包括以下步骤：
（1）将2-羟基苯并咪唑与甲醛水溶液混合加热，重结晶后将固体分散在二氯甲烷中，加入二氯亚砜，蒸干溶剂得化合物A；
（2）向化合物A中加入碳酸钾和咪唑，在乙腈中加热反应，抽滤得到化合物B；
（3）化合物A和化合物B于85~90℃在乙腈中加热，得到的沉淀化合物与NH4PF6在水-甲醇混合溶剂中进行离子交换，得咪唑鎓环蕃化合物C；
（4）将咪唑鎓环蕃化合物C与四氢噻吩氯化亚金在乙酸钠存在下在DMSO中反应，反应结束后加入甲醇析出化合物D；
（5）化合物D在DMF中与吡啶、三氟甲磺酸银反应得到催化剂E；
3.根据权利要求2所述的制备方法，其特征在于：步骤（5）中，用醚洗涤产物，所述醚是异丙醚、甲基叔丁基醚或乙醚。
4.根据权利要求3所述的制备方法，其特征在于：所述醚为乙醚。
5.权利要求1所述的烯烃光二聚催化剂在[2+2]光化学环加成反应中的应用，
或者
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