CN113354671A - 一种铜催化合成含硼与硫的烯烃化合物或含硼与硒的烯烃化合物的方法 - Google Patents
一种铜催化合成含硼与硫的烯烃化合物或含硼与硒的烯烃化合物的方法 Download PDFInfo
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- -1 olefin compound Chemical class 0.000 title claims abstract description 43
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000010949 copper Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 24
- 239000011593 sulfur Substances 0.000 title claims abstract description 24
- 239000011669 selenium Substances 0.000 title claims abstract description 19
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 125000003107 substituted aryl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 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 2
- 239000002585 base Substances 0.000 claims description 2
- WDODWFPDZYSKIA-UHFFFAOYSA-N benzeneselenol Chemical compound [SeH]C1=CC=CC=C1 WDODWFPDZYSKIA-UHFFFAOYSA-N 0.000 claims description 2
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000012973 diazabicyclooctane Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003958 selenols Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 1
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CACNDVVHWJTZHH-UHFFFAOYSA-N 2-phenylbenzeneselenol Chemical compound [SeH]C1=CC=CC=C1C1=CC=CC=C1 CACNDVVHWJTZHH-UHFFFAOYSA-N 0.000 description 2
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种铜催化合成含硼与硫的烯烃化合物或含硼与硒的烯烃化合物的方法,在铜催化下,炔丙醇酯类化合物与硫酚或硒酚反应,硫酚或硒酚反应完后直接向反应体系中加入联硼酸频那醇酯和甲醇继续反应得到含硼与硫或硒的烯烃。在催化条件下进行反应,由廉价易得的炔丙醇酯一锅法合成含硼与硫或硒的烯烃化合物,反应条件温和,所产生的废弃物少。合成方法操作简便实用易行,收率高,后处理简单,环境友好。
Description
技术领域
本发明涉及烯烃化合物化学合成技术领域,尤其涉及一种铜催化合成含硼与硫的烯烃化合物或含硼与硒的烯烃化合物的方法。
背景技术
含硫或硒化合物在药物、功能材料、高附加值精细化学品等领域具有重要的用途。含硼化合物是一种高效的偶联试剂,广泛用于碳碳键的形成。但是,含硫或硒的硼化合物合成方法较少,往往使用的原料合成繁琐或反应条件苛刻,本发明使用铜催化剂和廉价易得的原料炔丙醇酯,一锅合成含硼与硫的烯烃化合物或含硼与硒的烯烃化合物,是一种步骤简单、底物适用范围广泛的反应体系,具有重要的研究和应用价值。
发明内容
为解决上述技术问题,本发明提供一种铜催化合成含硼与硫的烯烃化合物或含硼与硒的烯烃化合物的方法。
本发明提供一种铜催化合成含硼与硫的烯烃化合物或含硼与硒的烯烃化合物的方法,与相关技术相比,本发明的技术方案如下:
一种铜催化合成含硼与硫的烯烃化合物的方法,其步骤为在铜催化下,炔丙醇酯类化合物与硫酚反应,然后向反应体系中加入联硼酸频那醇酯得到硼与硫的烯烃化合物A,其反应公式如下:
式中,取代基R1选自氢、碳原子数为1–8的烷基、芳基、取代芳基的至少一种,其中所述取代芳基选自氟、氯、溴、硝基、三氟甲基、碳原子数为1–4的烷基、碳原子数1–4的烷氧基中的至少一种;取代基R2选自甲基、乙基、叔丁基中的至少一种;取代基R3选自芳基、取代芳基中的至少一种,其中所述取代芳基选自氟、氯、溴、硝基、三氟甲基、碳原子数为1–4的烷基、碳原子数1–4的烷氧基中的至少一种。
进一步的,上述具体步骤为:
(1)在氮气保护下,将铜金属前体和配体加入有机溶剂,在室温反应30分钟得到催化剂溶液;
(2)在氮气保护下向所述催化剂溶液中依次加入炔丙基酯类化合物、硫酚、碱,搅拌1~30小时;
(3)加入联硼酸频那醇酯和甲醇继续搅拌1~30小时;
(4)反应结束后按常规分离方法进行产物分离即可得到含硼与硫烯烃化合物A。
进一步的,所述铜金属前体选自CuCl、CuBr、CuI、CuCl2、 CuBr2、Cu(OAc)2、CuTc、CuOAc、Cu(CH3CN)4PF6的至少一种。
进一步的,配体选自下列化合物的至少一种:
进一步的,有机溶剂选自四氢呋喃、甲苯、1,4-二氧六环、二氯甲烷、乙醚、甲基叔丁基醚中的至少一种。
进一步的,碱选自碳酸钠、碳酸钾、碳酸铯、叔丁醇钠、叔丁醇钾、氢氧化钠、氢氧化钾、Et3N、iPr2NEt、DBU、DABCO中的至少一种。
进一步的,投料比例为:铜的金属前体、配体、炔丙醇酯类化合物、硫酚或硒酚、碱、联硼酸频那醇酯、甲醇的摩尔比为:0.05~ 0.2:0.05~0.4:1~2:1~1.5:1~2:1~1.2:1~3。
进一步的,反应温度0~60℃。
一种铜催化合成含硼与硒的烯烃化合物的方法,其步骤为,在铜催化下,炔丙醇酯类化合物与硒酚反应,硫酚反应完后直接向反应体系中加入联硼酸频那醇酯得到硼与硒的烯烃化合物B,其反应公式如下:
式中,取代基R4为芳基或取代芳基的至少一种,其中所述取代芳基为氟、氯、溴、硝基、三氟甲基、碳原子数为1–4的烷基、碳原子数1–4的烷氧基中的至少一种。
本发明的有益效果如下:
1.在催化条件下进行反应,催化剂商业可得,反应操作简便实用,反应条件温和,所产生的废弃物少。
2.反应一锅法得到多取代、多官能团化、结构多样的含硼与硫的烯烃化合物或含硼与硒的烯烃化合物。
3.合成方法操作简便实用易行,收率高,后处理简单,环境友好,具有潜在的实际应用价值。
具体实施方式
为了进一步阐述本发明为达成预定目的所采取的技术手段及功效, 以下结合具体实施方式,对依据本发明提出的一种铜催化合成含硼与硫 的烯烃化合物或含硼与硒的烯烃化合物的方法进行详细说明。
有关本发明的前述及其他技术内容、特点及功效,在以下配合具体 实施方式详细说明中即可清楚地呈现。通过具体实施方式的说明,可对 本发明为达成预定目的所采取的技术手段及功效进行更加深入且具体 地了解。应当说明的是,在本文中,诸如第一和第二等之类的关系术语 仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定 要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。 而且,术语“包括”、“包含”或者任何其他变体意在涵盖非排他性的包 含,从而使得包括一系列要素的物品或者设备不仅包括那些要素,而且 还包括没有明确列出的其他要素。在没有更多限制的情况下,由语句 “包括一个……”限定的要素,并不排除在包括所述要素的物品或者设 备中还存在另外的相同要素。
实施例1
本实施例提供一种铜催化合成含硼与硫的烯烃化合物的方法,反应式为:
氮气保护下,在反应瓶中加入CuCl(1mg)和配体L18(4.9mg),然后加入有机溶剂甲苯(2mL),室温搅拌30分钟。然后在氮气保护下向反应瓶中加入炔丙醇酯1(0.3mmol)、对氯苯硫酚2(0.22 mmol)和碳酸铯(0.4mmol),在25℃搅拌反应,TLC监测对氯苯硫酚消失后,加入联硼酸频那醇酯(0.2mmol)和甲醇(0.6mmol)继续搅拌反应6小时,除去溶剂后直接柱层析分离得到含硼与硫的烯烃产物3。
在该实施例的方法中得到产物59mg,收率为77%,表征分析数据为:1H NMR(400MHz,CDCl3)δ7.38-7.34(m,2H),7.29-7.26 (m,7H),6.76(s,1H),3.78(d,J=0.8Hz,2H),1.32(s,12H). HRMS(ESI-MS)m/zcalcd for C21H24BClO2S(M+Na)+409.1171,found409.1178.
表1不同反应条件下合成化合物3
实施例2
本实施例提供一种铜催化合成含硼与硒的烯烃化合物的方法,反应式为:
氮气保护下,在反应瓶中加入CuOAc(1.2mg)和配体L21(6mg),然后加入有机溶剂1,4-二氧六环(2mL),室温搅拌30分钟。然后在氮气保护下向反应瓶中加入炔丙醇酯1(0.3mmol)、苯硒酚4(0.22 mmol)和碳酸铯(0.4mmol),在25℃搅拌反应,TLC监测苯硒酚消失后,加入联硼酸频那醇酯(0.2mmol)和甲醇(0.6mmol)继续搅拌反应24小时,除去溶剂后直接柱层析分离得到含硼与硒的烯烃产物5。
在该实施例的方法中得到产物64mg,收率为80%,表征分析数据为:1H NMR(400MHz,CDCl3)δ7.56-7.54(m,2H),7.26-7.19 (m,8H),6.55(s,1H),3.79(s,2H),1.30(s,12H).HRMS(ESI-MS) m/zcalcd for C21H25BO2Se(M+Na)+423.1005,found 423.1017.
表2不同反应条件下合成化合物5
entry | 铜金属前体 | 配体 | 碱 | 溶剂 | 5收率 |
1 | CuOAc | L10 | Cs<sub>2</sub>CO<sub>3</sub> | 1,4-二氧六环 | 83% |
2 | CuOAc | L10/L21 | Cs<sub>2</sub>CO<sub>3</sub> | 1,4-二氧六环 | 84% |
3 | CuI | L22 | Cs<sub>2</sub>CO<sub>3</sub> | 1,4-二氧六环 | 52% |
需要强调的是,上述1-5,L1-L22均为反应式中对应的化合物编号,无其他特殊含义。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其它相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (9)
2.根据权利要求1所述的一种铜催化合成含硼与硫的方法,其特征在于,具体步骤为:
(1)在氮气保护下,将铜金属前体和配体加入有机溶剂,在室温反应30分钟得到催化剂溶液;
(2)在氮气保护下向所述催化剂溶液中依次加入炔丙基酯类化合物、硫酚、碱,搅拌1~30小时;
(3)加入联硼酸频那醇酯和甲醇继续搅拌1~30小时;
(4)反应结束后按常规分离方法进行产物分离即可得到含硼与硫烯烃化合物A。
3.根据权利要求2所述的一种铜催化合成含硼与硫的烯烃化合物方法,其特征在于,所述铜金属前体选自CuCl、CuBr、CuI、CuCl2、CuBr2、Cu(OAc)2、CuTc、CuOAc、Cu(CH3CN)4PF6的至少一种。
5.根据权利要求2所述的一种铜催化合成含硼与硫的烯烃化合物方法,其特征在于,有机溶剂选自四氢呋喃、甲苯、1,4-二氧六环、二氯甲烷、乙醚、甲基叔丁基醚中的至少一种。
6.根据权利要求2所述的一种铜催化合成含硼与硫的烯烃化合物的方法,其特征在于,碱选自碳酸钠、碳酸钾、碳酸铯、叔丁醇钠、叔丁醇钾、氢氧化钠、氢氧化钾、Et3N、iPr2NEt、DBU、DABCO中的至少一种。
7.根据权利要求2所述的一种铜催化合成含硼与硫的烯烃化合物的方法,其特征在于,投料比例为:铜的金属前体、配体、炔丙醇酯类化合物、硫酚或硒酚、碱、联硼酸频那醇酯、甲醇的摩尔比为:0.05~0.2:0.05~0.4:1~2:1~1.5:1~2:1~1.2:1~3。
8.根据权利要求2所述的一种铜催化合成含硼与硫的烯烃化合物的方法,其特征在于,反应温度0~60℃。
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