CN115385876B - 一种光催化活化四氢呋喃α位C-H键构筑C-C键的方法 - Google Patents
一种光催化活化四氢呋喃α位C-H键构筑C-C键的方法 Download PDFInfo
- Publication number
- CN115385876B CN115385876B CN202110562873.1A CN202110562873A CN115385876B CN 115385876 B CN115385876 B CN 115385876B CN 202110562873 A CN202110562873 A CN 202110562873A CN 115385876 B CN115385876 B CN 115385876B
- Authority
- CN
- China
- Prior art keywords
- tetrahydrofuran
- solution
- bond
- alpha
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 82
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000004913 activation Effects 0.000 title claims abstract description 9
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 8
- 238000007146 photocatalysis Methods 0.000 title description 2
- -1 amine compound Chemical class 0.000 claims abstract description 46
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000002096 quantum dot Substances 0.000 claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 claims abstract description 10
- 238000010276 construction Methods 0.000 claims abstract description 5
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- ONQBUHWENXKHHP-UHFFFAOYSA-N 2-phenyl-3,4-dihydro-1h-isoquinoline Chemical compound C1CC2=CC=CC=C2CN1C1=CC=CC=C1 ONQBUHWENXKHHP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 abstract description 6
- 238000007259 addition reaction Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 36
- 239000001257 hydrogen Substances 0.000 description 36
- 229910052739 hydrogen Inorganic materials 0.000 description 36
- 238000001228 spectrum Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- OTAFHZMPRISVEM-UHFFFAOYSA-N chromone Chemical compound C1=CC=C2C(=O)C=COC2=C1 OTAFHZMPRISVEM-UHFFFAOYSA-N 0.000 description 22
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- MZGMTIBYFDHKAS-CMDGGOBGSA-N 2-[(e)-2-phenylethenyl]oxolane Chemical compound C1CCOC1\C=C\C1=CC=CC=C1 MZGMTIBYFDHKAS-CMDGGOBGSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000004777 chromones Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PPGNLHBXIQOECF-UHFFFAOYSA-N 2-(2-naphthalen-2-ylethenyl)oxolane Chemical compound C1CCOC1C=CC1=CC=C(C=CC=C2)C2=C1 PPGNLHBXIQOECF-UHFFFAOYSA-N 0.000 description 2
- FKESZOSYQRABRX-VMPITWQZSA-N 2-[(E)-2-(4-fluorophenyl)ethenyl]oxolane Chemical compound FC1=CC=C(C=C1)/C=C/C1OCCC1 FKESZOSYQRABRX-VMPITWQZSA-N 0.000 description 2
- YRPHSKRQBPROAN-RMKNXTFCSA-N 2-[(e)-2-(4-methoxyphenyl)ethenyl]oxolane Chemical compound C1=CC(OC)=CC=C1\C=C\C1OCCC1 YRPHSKRQBPROAN-RMKNXTFCSA-N 0.000 description 2
- LWBKDGQFSFQSRC-UHFFFAOYSA-N 2-[2-(2-fluorophenyl)ethenyl]oxolane Chemical compound FC1=CC=CC=C1C=CC1OCCC1 LWBKDGQFSFQSRC-UHFFFAOYSA-N 0.000 description 2
- WLKOTLPBWJKGTE-UHFFFAOYSA-N 2-[2-(2-methoxyphenyl)ethenyl]oxolane Chemical compound COc1ccccc1C=CC1CCCO1 WLKOTLPBWJKGTE-UHFFFAOYSA-N 0.000 description 2
- SRYUSLRZJFJMNN-UHFFFAOYSA-N 2-[2-(3-fluorophenyl)ethenyl]oxolane Chemical compound Fc1cccc(C=CC2CCCO2)c1 SRYUSLRZJFJMNN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RVDOYUFNRDGYGU-UHFFFAOYSA-N 1-bromo-2-ethynylbenzene Chemical group BrC1=CC=CC=C1C#C RVDOYUFNRDGYGU-UHFFFAOYSA-N 0.000 description 1
- TZDXNFAAJNEYIO-UHFFFAOYSA-N 1-bromo-3-ethynylbenzene Chemical group BrC1=CC=CC(C#C)=C1 TZDXNFAAJNEYIO-UHFFFAOYSA-N 0.000 description 1
- LTLVZQZDXQWLHU-UHFFFAOYSA-N 1-bromo-4-ethynylbenzene Chemical group BrC1=CC=C(C#C)C=C1 LTLVZQZDXQWLHU-UHFFFAOYSA-N 0.000 description 1
- DGLHLIWXYSGYBI-UHFFFAOYSA-N 1-chloro-2-ethynylbenzene Chemical group ClC1=CC=CC=C1C#C DGLHLIWXYSGYBI-UHFFFAOYSA-N 0.000 description 1
- GRBJPHPMYOUMJV-UHFFFAOYSA-N 1-chloro-3-ethynylbenzene Chemical group ClC1=CC=CC(C#C)=C1 GRBJPHPMYOUMJV-UHFFFAOYSA-N 0.000 description 1
- LFZJRTMTKGYJRS-UHFFFAOYSA-N 1-chloro-4-ethynylbenzene Chemical group ClC1=CC=C(C#C)C=C1 LFZJRTMTKGYJRS-UHFFFAOYSA-N 0.000 description 1
- ZNTJVJSUNSUMPP-UHFFFAOYSA-N 1-ethyl-4-ethynylbenzene Chemical group CCC1=CC=C(C#C)C=C1 ZNTJVJSUNSUMPP-UHFFFAOYSA-N 0.000 description 1
- YFPQIXUNBPQKQR-UHFFFAOYSA-N 1-ethynyl-2-fluorobenzene Chemical group FC1=CC=CC=C1C#C YFPQIXUNBPQKQR-UHFFFAOYSA-N 0.000 description 1
- UFOVULIWACVAAC-UHFFFAOYSA-N 1-ethynyl-2-methoxybenzene Chemical group COC1=CC=CC=C1C#C UFOVULIWACVAAC-UHFFFAOYSA-N 0.000 description 1
- PTRUTZFCVFUTMW-UHFFFAOYSA-N 1-ethynyl-3-fluorobenzene Chemical group FC1=CC=CC(C#C)=C1 PTRUTZFCVFUTMW-UHFFFAOYSA-N 0.000 description 1
- ZASXCTCNZKFDTP-UHFFFAOYSA-N 1-ethynyl-3-methoxybenzene Chemical group COC1=CC=CC(C#C)=C1 ZASXCTCNZKFDTP-UHFFFAOYSA-N 0.000 description 1
- RENYIDZOAFFNHC-UHFFFAOYSA-N 1-ethynyl-3-methylbenzene Chemical group CC1=CC=CC(C#C)=C1 RENYIDZOAFFNHC-UHFFFAOYSA-N 0.000 description 1
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical group FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 description 1
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 description 1
- ZSYQVVKVKBVHIL-UHFFFAOYSA-N 1-tert-butyl-4-ethynylbenzene Chemical group CC(C)(C)C1=CC=C(C#C)C=C1 ZSYQVVKVKBVHIL-UHFFFAOYSA-N 0.000 description 1
- ZQRNHKHJHXASQM-UHFFFAOYSA-N 2-(2-chlorophenyl)oxolane Chemical compound ClC1=CC=CC=C1C1OCCC1 ZQRNHKHJHXASQM-UHFFFAOYSA-N 0.000 description 1
- SWXNHTMSSUGJAX-UHFFFAOYSA-N 2-(4-chlorophenyl)oxolane Chemical compound C1=CC(Cl)=CC=C1C1OCCC1 SWXNHTMSSUGJAX-UHFFFAOYSA-N 0.000 description 1
- WGGOEMYUAXWYMS-BQYQJAHWSA-N 2-[(E)-2-(2-chlorophenyl)ethenyl]oxolane Chemical compound ClC1=C(/C=C/C2OCCC2)C=CC=C1 WGGOEMYUAXWYMS-BQYQJAHWSA-N 0.000 description 1
- HWXYFDJJEUJWFK-VMPITWQZSA-N 2-[(E)-2-(4-chlorophenyl)ethenyl]oxolane Chemical compound ClC1=CC=C(/C=C/C2OCCC2)C=C1 HWXYFDJJEUJWFK-VMPITWQZSA-N 0.000 description 1
- SKEBZANULWMITF-UHFFFAOYSA-N 2-[2-(2-bromophenyl)ethenyl]oxolane Chemical compound Brc1ccccc1C=CC1CCCO1 SKEBZANULWMITF-UHFFFAOYSA-N 0.000 description 1
- POBIMSCWRYFOIO-UHFFFAOYSA-N 2-[2-(3-chlorophenyl)ethenyl]oxolane Chemical compound ClC1=CC=CC(C=CC2OCCC2)=C1 POBIMSCWRYFOIO-UHFFFAOYSA-N 0.000 description 1
- IZXPFTLEVNQLGD-UHFFFAOYSA-N 2-ethynylnaphthalene Chemical compound C1=CC=CC2=CC(C#C)=CC=C21 IZXPFTLEVNQLGD-UHFFFAOYSA-N 0.000 description 1
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 description 1
- UKYNXFCCXVEYKJ-VMPITWQZSA-N BrC1=CC=C(/C=C/C2OCCC2)C=C1 Chemical compound BrC1=CC=C(/C=C/C2OCCC2)C=C1 UKYNXFCCXVEYKJ-VMPITWQZSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/16—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开一种光催化活化四氢呋喃α位C‑H键构筑C‑C键的方法,包括以下步骤:1)将光催化剂和四氢呋喃加入溶剂中,得溶液A;2)将不饱和烃或胺类化合物加入溶液A中,得溶液B;3)在惰性气氛中,用可见光源照射溶液B,实现四氢呋喃α位C‑C键的构筑。本发明首次实现了通过可见光驱动量子点催化四氢呋喃α位C‑H键活化为醚类自由基,进而与不饱和烃发生加成反应,或者与胺类化合物发生偶联,实现四氢呋喃α位C‑C键的构筑,制备得到2‑烷基/烯基四氢呋喃衍生物。且该反应条件温和,在室温常压下光源照射量子点催化剂就可以实现;同时反应物简单,不需要强氧化剂,步骤少,原子经济。
Description
技术领域
本发明涉及催化合成技术领域。更具体地,涉及一种光催化活化四氢呋喃α位C-H键构筑C-C键的方法。
背景技术
2-烷基/烯基四氢呋喃衍生物广泛分布在许多具有生物活性的天然产物以及药物制剂中。活化四氢呋喃(THF)的氧邻位C(sp3)-H键得到醚类自由基,进而对不饱和烃进行加成,或者与胺进行偶联是制备2-烷基/烯基四氢呋喃衍生物的最直接途径之一。然而,THF的化学性质稳定,在学术研究和工业生产中被广泛用作溶剂。特别是,较高的键离解能(BDE=92.0kcal/mol),低极性的C(sp3)-H键和较高还原电位(E1/2 red=+1.75v vs SCE),使得直接活化THF中的α-C(sp3)-H键成为一项具有挑战性的任务。
可见光催化由于其温和的特性,被认为是合成多种有价值化合物的理想方法。为了实现光催化四氢呋喃的活化,传统方法通常需要使用光催化剂与强氧化剂(如过氧化物和过硫酸盐)或镍催化剂结合使用。烷氧自由基或原位生成的氯自由基可以作为氢原子转移(HAT)试剂,用于活化四氢呋喃α-C-H键。例如,2015年,王志刚课题组利用曙红Y为光敏剂、叔丁基过氧化氢为氧化剂活化四氢呋喃,并完成了同类底物的烯烃化反应(Li,J.;Zhang,J.;Tan,H.;Wang,D.Z.,Org.Lett.2015,17,2522.)。但是,化学计量的强氧化剂和过渡金属催化剂的使用导致了较高成本和副产物的生成。2018年,吴杰等人用曙红Y作光敏剂,可见光照射下能够在60℃左右实现THF和苯乙炔的氧邻位烯基化反应(Fan,X.Z.;Rong,J.W.;Wu,H.L.;Zhou,Q.;Deng,H.P.;Tan,J.D.;Xue,C.W.;Wu,L.Z.;Tao,H.R.;Wu,J.,Angew.Chem.,Int.Ed.2018,57,8514.)。此方法必须要求加热条件才能使目标转化顺利进行。
因此,需要提供一种反应条件温和、节省成本以及无副产物生成的实现活化四氢呋喃α位C-H键构筑C-C键的方法。
发明内容
本发明的一个目的在于提供一种光催化活化四氢呋喃α位C-H键构筑C-C键的方法,该方法不需要强氧化剂,温和条件下实现四氢呋喃α位C-C键构筑,合成含氧杂环类产物。
为达到上述目的,本发明采用下述技术方案:
一种光催化活化四氢呋喃α位C-H键构筑C-C键的方法,包括以下步骤:
1)将光催化剂和四氢呋喃加入溶剂中,得溶液A;
2)将不饱和烃或胺类化合物加入溶液A中,得溶液B;
3)在惰性气氛中,用可见光源照射溶液B,实现四氢呋喃α位C-C键的构筑。
本发明中,四氢呋喃α位C-H键被活化为醚类自由基,进而与不饱和烃发生加成反应,或者与胺类化合物发生偶联,实现四氢呋喃α位C-C键构筑,制备得到2-烷基/烯基四氢呋喃衍生物。该反应条件温和,是在惰性气体、常温常压下进行的,且反应过程中没有使用强氧化剂,成本低廉且无副产物生成。
优选地,所述不饱和烃包括苯乙炔类化合物或色酮类化合物。
进一步优选地,所述苯乙炔类化合物为或式1所示化合物:
式1中,R1、R2、R3为H;或
R1为F、Cl、Br或OMe,R2、R3为H;或
R2为F、Cl、Br或OMe,R1、R3为H;或
R3为F、Cl、Br或OMe,R1、R2为H;或
R2为CO2Me或Me,R1、R3为H;或
R3为CO2Me或Me,R1、R2为H;或
R3为Et,R1、R2为H;或
R3为tBu,R1、R2为H。
进一步优选地,所述色酮类化合物为或式2所示化合物:
式2中,X1、X2为H;或
X1为CH3、F、Cl或Br,X2为H;或
X1为Cl,X2为CH3;或
X2为OCH3或OH,X1为H。
优选地,所述胺类化合物包括N-苯基四氢异喹啉类化合物、N-取代4,5,6,7-四氢噻吩并[3,2-c]吡啶类化合物或芳基甘氨酸酯类化合物。
进一步优选地,所述N-苯基四氢异喹啉类化合物的结构式如式3所示:
式3中,T1、T2、T3、T4、T5为H;或
T1为CH3、CH2CH3、OCH3、Ph、F、Cl或CF3,T2、T3、T4、T5为H;或
T2为CH3,T1、T3、T4、T5为H;或
T1和T2为CH3,T3、T4、T5为H;或
T3为OCH3,T1、T2、T4、T5为H;或
T4为OCH3,T1、T2、T3、T5为H;或
T4和T5为OCH3,T1、T2、T3为H。
进一步优选地,所述N-取代4,5,6,7-四氢噻吩并[3,2-c]吡啶类化合物的结构式如4所示:
式4中,Y1、Y2、Y3为H;或
Y1为CH(CH3)2或OCH3,Y2、Y3为H;或
Y2为CH3,Y1、Y3为H;或
Y3为OCH3,Y1、Y2为H。
进一步优选地,所述芳基甘氨酸酯类化合物的结构式如式5所示:
式5中,Z1、Z2为H,Z3为CH2CH3;或
Z1为CH3、OCH3、CF3、Ph或F,Z2为H,Z3为CH2CH3;或
Z1为H,Z2为Ph,Z3为CH2CH3;或
Z1、Z2为H,Z3为CH2Ph或C(CH3)3。
本发明中的溶剂只是为了给反应物提供溶液环境,本领域技术人员有能力选择合适的溶剂,本发明对此不作限制。优选地,所述溶剂选自丙酮、DMSO、CHCl3、CH3OH、DMF或CH3CN中的一种或多种。
优选地,所述光催化剂选自选自下列量子点中的一种或多种:CdSe、CdS、CdTe、ZnSe、ZnS、CdSe/ZnS、CdSe/ZnO、CdSe/CdS、CdTe/CdSe、CdS/ZnSe、CdS/ZnTe、ZnSe/CdS或CuInS;量子点光催化剂具有广泛的吸光特性、对氧化还原反应较强的驱动力和丰富的反应位点,且与与广泛使用的Ir或Ru光催化剂相比,量子点通常更廉价,容易制备并可重复使用。
优选地,溶液A中光催化剂的溶度为零到饱和摩尔浓度,且不包括零;进一步优选为1×10-7M~1×10-4M。
优选地,溶液A中还包括有添加剂;所述添加剂为K2HPO4、NaHCO3、K2CO3、CH3COOH、HCOOH、苯甲酸中的一种或多种。添加剂有利于加快反应速率,提高产物得率。
优选地,溶液B中四氢呋喃与不饱和烃的摩尔比为1:(0.01~1);四氢呋喃与胺类化合物的摩尔比为1:(0.01~1)。
所述不饱和烃或胺类化合物在溶液B中的摩尔浓度在零到饱和摩尔浓度之间,且不包括零;
优选地,溶液B中不饱和烃的摩尔浓度为0.001M~10M;溶液B中胺类化合物的摩尔浓度为0.001M~10M。
本发明中可见光源为能够提供稳定可见光的光源,本发明对其类型不作限制,例如,太阳光、LED灯、中压汞灯、高压汞灯或氙灯。
本发明的有益效果如下:
本发明首次实现了通过可见光驱动量子点催化四氢呋喃α位C-H键活化为醚类自由基,进而与不饱和烃发生加成反应,或者与胺类化合物发生偶联,实现四氢呋喃α位C-C键构筑,制备得到2-烷基/烯基四氢呋喃衍生物。且该反应条件温和,在室温常压下光源照射量子点催化剂就可以实现,不需要高温高压等苛刻的反应条件;同时反应物简单,不需要强氧化剂,步骤少,原子经济。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1示出本发明实施例1中产物2-苯乙烯基四氢呋喃的氢谱图。
图2示出本发明实施例2中产物2-(2-氟苯乙烯基)四氢呋喃的氢谱图。
图3示出本发明实施例3中产物2-(3-氟苯乙烯基)四氢呋喃的氢谱图。
图4示出本发明实施例4中产物2-(4-氟苯乙烯基)四氢呋喃的氢谱图。
图5示出本发明实施例5中产物2-(2-氯苯乙烯基)四氢呋喃的氢谱图。
图6示出本发明实施例6中产物2-(3-氯苯乙烯基)四氢呋喃的氢谱图。
图7示出本发明实施例7中产物2-(4-氯苯乙烯基)四氢呋喃的氢谱图。
图8示出本发明实施例8中产物2-(2-溴苯乙烯基)四氢呋喃的氢谱图。
图9示出本发明实施例9中产物2-(3-溴苯乙烯基)四氢呋喃的氢谱图。
图10示出本发明实施例10中产物2-(4-溴苯乙烯基)四氢呋喃的氢谱图。
图11示出本发明实施例11中产物2-(2-甲氧基苯乙烯基)四氢呋喃的氢谱图。
图12示出本发明实施例12中产物2-(3-甲氧基苯乙烯基)四氢呋喃的氢谱图。
图13示出本发明实施例13中产物2-(4-甲氧基苯乙烯基)四氢呋喃的氢谱图。
图14示出本发明实施例14中产物3-(2-(四氢呋喃-2-基)乙烯基)苯甲酸甲酯的氢谱图。
图15示出本发明实施例15中产物4-(2-(四氢呋喃-2-基)乙烯基)苯甲酸甲酯的氢谱图。
图16示出本发明实施例16中产物2-(3-甲基苯乙烯)四氢呋喃的氢谱图。
图17示出本发明实施例17中产物2-(4-甲基苯乙烯)四氢呋喃的氢谱图。
图18示出本发明实施例18中产物2-(4-乙基苯乙烯)四氢呋喃的氢谱图。
图19示出本发明实施例19中产物2-(4-叔丁基苯乙烯)四氢呋喃的氢谱图。
图20示出本发明实施例20中产物(2-(萘-2-基)乙烯基)四氢呋喃的氢谱图。
图21示出本发明实施例21中产物(S)-2-(((S)-四氢呋喃-2-基)苯并吡喃-4-酮的氢谱图。
图22示出本发明实施例22中产物(S)-6-甲基-2-((S)-四氢呋喃-2-基)苯并吡喃-4-酮的氢谱图。
图23示出本发明实施例23中产物(S)-7-甲氧基-2-((S)-四氢呋喃-2-基)苯并吡喃-4-酮的氢谱图。
图24示出本发明实施例24中产物(S)-7-羟基-2-((S)-四氢呋喃-2-基)苯并吡喃-4-酮的氢谱图。
图25示出本发明实施例25中产物(S)-6-氟-2-((S)-四氢呋喃-2-基)苯并吡喃-4-酮的氢谱图。
图26示出本发明实施例26中产物(S)-6-氯-2-((S)-四氢呋喃-2-基)苯并吡喃-4-酮的氢谱图。
图27示出本发明实施例27中产物(S)-6-溴-2-((S)-四氢呋喃-2-基)苯并吡喃-4-酮的氢谱图。
图28示出本发明实施例28中产物(S)-6-氯-7-甲基-2-((S)-四氢呋喃-2-基)苯并吡喃-4-酮的氢谱图。
图29示出本发明实施例29中产物(S)-1,3-二苯基-3-((S)-四氢呋喃-2-基)丙-1-酮的氢谱图。
图30示出本发明实施例30中产物(R)-2-苯基-1-((S)-四氢呋喃-2-基)-1,2,3,4-四氢异喹啉的氢谱图。
图31示出本发明实施例31中产物(R)-1-((S)-四氢呋喃-2-基)-2-(对甲苯基)-1,2,3,4-四氢异喹啉的氢谱图。
图32示出本发明实施例32中产物(R)-1-((S)-四氢呋喃-2-基)-2-(间甲苯基)-1,2,3,4-四氢异喹啉的氢谱图。
图33示出本发明实施例33中产物(R)-2-(3,4-二甲基苯基)-1-((S)-四氢呋喃-2-基)-1,2,3,4-四氢异喹啉的氢谱图。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例和附图对本发明做进一步的说明。附图中相似的部件以相同的附图标记进行表示。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
本发明中光敏剂参照文献报道的方法制备(Li,Z.-J.;Fan,X.-B.;Li,X.-B.;Li,J.-X.;Zhan,F.;Tao,Y.;Zhang,X.-Y.;Kong,Q.-Y.;Zhao,N.-J.;Zhang,J.-P.;Ye,C.;Gao,Y.-J.;Wang,X.-Z.;Meng,Q.-Y.;Feng,K.;Chen,B.;Tung,C.-H.;Wu,L.-Z.,J.Mater.Chem.A 2017,5,10365.)。
实施例1
化合物2-苯乙烯基四氢呋喃的合成,步骤如下:
1)取4mL浓度为8.0×10-5mol/L的CdSe/CdS量子点水溶液,加入0.1mL浓度为2mol/L的硝酸的混合溶液,将该混合溶液在离心机上离心分离,除去上层水溶液,得到固体物质;此步骤的目的是(1)除去量子点表面的配体;(2)通过离心沉淀的方法除去溶剂水,得到固体物质,利于用其他溶剂进行研究。
2)将步骤1)中的固体物质加入2mL的乙腈,超声2分钟,加入2mL四氢呋喃,然后加入0.1mmol K2HPO4,得到溶液A;
3)向溶液A中加入0.05mmol苯乙炔,得到溶液B;
4)在氩气保护下,采用LED蓝光照射溶液B 24h;
5)旋干法除去反应溶剂,再用硅胶过柱分离,得到产物2-苯乙烯基四氢呋喃。
其中产物的收率为36%。核磁氢谱、碳谱鉴定产物为2-苯乙烯基四氢呋喃。
对比例1
对比例1中反应过程与实施例1相比较,不同之处在于步骤4)中的反应过程是在空气中进行的,结果发现反应不能进行,说明本发明四氢呋喃α位C-C键构筑反应必须是在惰性气氛中才能进行。
实施例2-20
在实施例2-20中,反应过程与实施例1完全相同,不同的是使用表1所示苯乙炔类化合物代替了实施例1中的苯乙炔,其产物具体请见表1:
表1实施例2-20中不同的苯乙炔类反应物以及对应的产物
实施例编号 | 苯乙炔类化合物 | 收率(%) | 产物名称 |
2 | 2-氟苯乙炔 | 60 | 2-(2-氟苯乙烯基)四氢呋喃 |
3 | 3-氟苯乙炔 | 58 | 2-(3-氟苯乙烯基)四氢呋喃 |
4 | 4-氟苯乙炔 | 40 | 2-(4-氟苯乙烯基)四氢呋喃 |
5 | 2-氯苯乙炔 | 54 | 2-(2-氯苯乙烯基)四氢呋喃 |
6 | 3-氯苯乙炔 | 56 | 2-(3-氯苯乙烯基)四氢呋喃 |
7 | 4-氯苯乙炔 | 63 | 2-(4-氯苯乙烯基)四氢呋喃 |
8 | 2-溴苯乙炔 | 64 | 2-(2-溴苯乙烯基)四氢呋喃 |
9 | 3-溴苯乙炔 | 52 | 2-(3-溴苯乙烯基)四氢呋喃 |
10 | 4-溴苯乙炔 | 59 | 2-(4-溴苯乙烯基)四氢呋喃 |
11 | 2-甲氧基苯乙炔 | 23 | 2-(2-甲氧基苯乙烯基)四氢呋喃 |
12 | 3-甲氧基苯乙炔 | 25 | 2-(3-甲氧基苯乙烯基)四氢呋喃 |
13 | 4-甲氧基苯乙炔 | 28 | 2-(4-甲氧基苯乙烯基)四氢呋喃 |
14 | 3-乙炔基苯甲酸甲酯 | 56 | 3-(2-(四氢呋喃-2-基)乙烯基)苯甲酸甲酯 |
15 | 4-乙炔基苯甲酸甲酯 | 44 | 4-(2-(四氢呋喃-2-基)乙烯基)苯甲酸甲酯 |
16 | 3-甲基苯乙炔 | 33 | 2-(3-甲基苯乙烯)四氢呋喃 |
17 | 4-甲基苯乙炔 | 30 | 2-(4-甲基苯乙烯)四氢呋喃 |
18 | 4-乙基苯乙炔 | 24 | 2-(4-乙基苯乙烯)四氢呋喃 |
19 | 4-叔丁基苯乙炔 | 26 | 2-(4-(叔丁基)苯乙烯基)四氢呋喃 |
20 | 2-乙炔基萘 | 34 | (2-(萘-2-基)乙烯基)四氢呋喃 |
实施例21
化合物(S)-2-(((S)-四氢呋喃-2-基)苯并吡喃-4-酮的合成,步骤如下:
1)取4mL浓度为8.0×10-5mol/L的CdSe量子点水溶液,加入0.1mL浓度为2mol/L的硝酸的混合溶液,将该混合溶液在离心机上离心分离,除去上层水溶液,得到固体物质;此步骤的目的是(1)除去量子点表面的配体;(2)通过离心沉淀的方法除去溶剂水,得到固体物质,利于用其他溶剂进行研究。
2)将步骤1)中的固体物质加入4mL的乙腈,超声2分钟,加入5mmol四氢呋喃,再加入0.2mmol CH3COOH,得到溶液A;
3)向溶液A中加入0.1mmol色酮,得到溶液B;
4)在氩气保护下,采用LED蓝光照射溶液B12h;
5)旋干法除去反应溶剂,再用硅胶过柱分离,得到产物(S)-2-(((S)-四氢呋喃-2-基)苯并吡喃-4-酮。
其中产物的收率为76%。核磁氢谱、碳谱鉴定产物为(S)-2-(((S)-四氢呋喃-2-基)苯并吡喃-4-酮。
实施例22-29
在实施例22-29中,反应过程与实施例21完全相同,不同的是使用表2所示色酮类化合物代替了实施例21中的色酮,其产物具体请见表2:
表2实施例22-29中不同的色酮类反应物以及对应的产物
实施例30
化合物(R)-2-苯基-1-((S)-四氢呋喃-2-基)-1,2,3,4-四氢异喹啉的合成,步骤如下:
1)取4mL浓度为8.0×10-5mol/L的CdSe量子点水溶液,加入0.1mL浓度为2mol/L的硝酸的混合溶液,将该混合溶液在离心机上离心分离,除去上层水溶液,得到固体物质;此步骤的目的是(1)除去量子点表面的配体;(2)通过离心沉淀的方法除去溶剂水,得到固体物质,利于用其他溶剂进行研究。
2)将步骤1)中的固体物质加入5mL的四氢呋喃,超声2分钟,0.2mmol苯甲酸,得到溶液A;
3)然后向溶液A中加入0.1mmol N-苯基四氢异喹啉,得到溶液B;
4)在氩气保护下,采用LED蓝光照射溶液B16h;
5)旋干法除去反应溶剂,再用硅胶过柱分离,得到产物(R)-2-苯基-1-((S)-四氢呋喃-2-基)-1,2,3,4-四氢异喹啉。
其中产物的收率为88%。核磁氢谱、碳谱鉴定产物为(R)-2-苯基-1-((S)-四氢呋喃-2-基)-1,2,3,4-四氢异喹啉。
实施例31-57
在实施例31-57中,反应过程与实施例30完全相同,不同的是使用表3所示胺类化合物代替了实施例30中的N-苯基四氢异喹啉,其产物具体请见表3:
表3实施例31-57中不同的胺类反应物以及对应的产物
实施例58
实施例58中反应过程与实施例1相比较,不同之处在于步骤2)中未添加K2HPO4,结果发现反应可以进行,能够生成2-苯乙烯基四氢呋喃,但产率较低,说明添加剂有利于提高反应速率,提高产物得率。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (7)
1.一种光催化活化四氢呋喃α位C-H键构筑C-C键的方法,其特征在于,包括以下步骤:
1)将光催化剂和四氢呋喃加入溶剂中,得溶液A;
2)将不饱和烃或胺类化合物加入溶液A中,得溶液B;
3)在惰性气氛中,用可见光源照射溶液B,实现四氢呋喃α位C-C键的构筑;
其中,所述光催化剂选自下列量子点中的一种或多种:CdSe/CdS、CdSe;
所述不饱和烃选自下述所示中的一种:
式1中,R1、R2、R3为H;或
R1为F、Cl、Br或OMe,R2、R3为H;或
R2为F、Cl、Br或OMe,R1、R3为H;或
R3为F、Cl、Br或OMe,R1、R2为H;或
R2为CO2Me或Me,R1、R3为H;或
R3为CO2Me或Me,R1、R2为H;或
R3为Et,R1、R2为H;或
R3为tBu,R1、R2为H;
式2中,X1、X2为H;或
X1为CH3、F、Cl或Br,X2为H;或
X1为Cl,X2为CH3;或
X2为OCH3或OH,X1为H;
所述胺类化合物选自N-苯基四氢异喹啉。
2.根据权利要求1所述的方法,其特征在于,所述溶剂选自丙酮、DMSO、CHCl3、CH3OH、DMF或CH3CN中的一种或多种。
3.根据权利要求1所述的方法,其特征在于,溶液A中光催化剂的溶度为零到饱和摩尔浓度,且不包括零。
4.根据权利要求1所述的方法,其特征在于,溶液A中还包括有添加剂,所述添加剂为K2HPO4、NaHCO3、K2CO3、CH3COOH、HCOOH、苯甲酸中的一种或多种。
5.根据权利要求1所述的方法,其特征在于,溶液B中四氢呋喃与不饱和烃的摩尔比为1:(0.01~1);四氢呋喃与胺类化合物的摩尔比为1:(0.01~1)。
6.根据权利要求1所述的方法,其特征在于,溶液B中不饱和烃的摩尔浓度为0.001M~10M;溶液B中胺类化合物的摩尔浓度为0.001M~10M。
7.根据权利要求1所述的方法,其特征在于,所述可见光源选自太阳光、LED灯、中压汞灯、高压汞灯或氙灯。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110562873.1A CN115385876B (zh) | 2021-05-24 | 2021-05-24 | 一种光催化活化四氢呋喃α位C-H键构筑C-C键的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110562873.1A CN115385876B (zh) | 2021-05-24 | 2021-05-24 | 一种光催化活化四氢呋喃α位C-H键构筑C-C键的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115385876A CN115385876A (zh) | 2022-11-25 |
CN115385876B true CN115385876B (zh) | 2024-01-30 |
Family
ID=84114396
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110562873.1A Active CN115385876B (zh) | 2021-05-24 | 2021-05-24 | 一种光催化活化四氢呋喃α位C-H键构筑C-C键的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115385876B (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108299261A (zh) * | 2018-03-19 | 2018-07-20 | 中国科学院理化技术研究所 | 一种通过c-h键直接官能团化合成烯丙基硫化物的方法 |
-
2021
- 2021-05-24 CN CN202110562873.1A patent/CN115385876B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108299261A (zh) * | 2018-03-19 | 2018-07-20 | 中国科学院理化技术研究所 | 一种通过c-h键直接官能团化合成烯丙基硫化物的方法 |
Non-Patent Citations (3)
Title |
---|
"Co-Catalyzed C(sp3)-H Oxidative Coupling of Glycine and Peptide Derivatives";Marcos San Segundo等;《Organic Letters》;第19卷;第5288-5291页 * |
"Photoredox Oxo-C(sp3)-H Bond Functionalization via in Situ Cu(I)-Acetylide Catalysis";Zi-Qi Song等;《Organic Letters》;第22卷;第832-836页 * |
Zi-Qi Song等."Photoredox Oxo-C(sp3)-H Bond Functionalization via in Situ Cu(I)-Acetylide Catalysis".《Organic Letters》.2020,第22卷第832-836页. * |
Also Published As
Publication number | Publication date |
---|---|
CN115385876A (zh) | 2022-11-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Koike et al. | Photoinduced oxyamination of enamines and aldehydes with TEMPO catalyzed by [Ru (bpy) 3] 2+ | |
JP4977353B2 (ja) | シクロブタンテトラカルボキシレート化合物及びその製造方法 | |
Dumur | Recent advances on ferrocene-based photoinitiating systems | |
CN109734666B (zh) | 一种二氧化碳促进和无光催化剂光诱导合成吲唑啉酮类化合物制备方法 | |
Ho et al. | Green organophotocatalysis. TiO 2-induced enantioselective α-oxyamination of aldehydes | |
CN1950373A (zh) | 采用微波制备甘脲和葫芦脲的方法 | |
CN101899022B (zh) | 一种仿生催化丙烯环氧化制备环氧丙烷的方法 | |
Mobinikhaledi et al. | Microwave-assisted efficient synthesis of azlactone derivatives using 2-aminopyridine-functionalized sphere SiO2 nanoparticles as a reusable heterogeneous catalyst | |
CN113461597B (zh) | 一种尼拉帕尼中间体的制备方法 | |
CN115385876B (zh) | 一种光催化活化四氢呋喃α位C-H键构筑C-C键的方法 | |
Hosseini-Sarvari et al. | Solar and visible-light active nano Ni/gC 3 N 4 photocatalyst for carbon monoxide (CO) and ligand-free carbonylation reactions | |
Zhang et al. | Halogen bond promoted aryl migration of allylic alcohols under visible light irradiation | |
WO2000073308A3 (en) | Bacteriochlorins and bacteriopurpurins useful as photoselective compounds for photodynamic therapy and a process for their production | |
Sportelli et al. | Graphitic carbon nitride as photocatalyst for the direct formylation of anilines | |
CN113816899B (zh) | 一种碳材料催化氧化取代的芳香类化合物生成酮或酯的方法 | |
Chung et al. | Topochemical induction to an alternating zigzag-linear and" syndiotactic" chain structure in the course of [2+ 2] photoreaction of alkyl. alpha.-cyano-4-[2-(2-pyridyl) ethenyl] cinnamate crystals | |
Nazeri et al. | Chemical CO 2 fixation using a green biocatalytic system based on Ugi conjugated cobalt phthalocyanine on cellulose | |
EP4121404A1 (en) | An improved process for photocatalytic hydrocarboxylation of methanol with co2 to produce acetic acid | |
CN105777815A (zh) | 二价锇配合物及其制备方法和应用 | |
CN108558665B (zh) | 一种可见光激发二硫醚催化制备α-羟基-β-二羰基化合物的方法 | |
CN105001183A (zh) | 一种联产环氧丙烷和糠酸的方法 | |
CN110938079B (zh) | 一种螺环氧吲哚衍生物及其制备方法 | |
ES2885530T3 (es) | Método para preparar un catalizador | |
CN111793040B (zh) | 一种2-取代苯并噻唑的制备方法 | |
Lal et al. | Allylsilane as a versatile handle in photoredox catalysis |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB03 | Change of inventor or designer information | ||
CB03 | Change of inventor or designer information |
Inventor after: Wu Chizhu Inventor after: Song Ziqi Inventor after: Qiao Jia Inventor after: Tong Zhenhe Inventor before: Song Ziqi Inventor before: Wu Chizhu Inventor before: Qiao Jia Inventor before: Tong Zhenhe |
|
GR01 | Patent grant | ||
GR01 | Patent grant |