CN115925544A - 一种铁催化氧化环叔醇开环丙烯酸酯化的方法 - Google Patents
一种铁催化氧化环叔醇开环丙烯酸酯化的方法 Download PDFInfo
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- CN115925544A CN115925544A CN202211648014.5A CN202211648014A CN115925544A CN 115925544 A CN115925544 A CN 115925544A CN 202211648014 A CN202211648014 A CN 202211648014A CN 115925544 A CN115925544 A CN 115925544A
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000007142 ring opening reaction Methods 0.000 title claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 33
- 125000003158 alcohol group Chemical group 0.000 title claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 13
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- 230000032050 esterification Effects 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- 239000000758 substrate Substances 0.000 claims abstract description 77
- -1 acrylate compound Chemical class 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 150000001413 amino acids Chemical class 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
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- 150000003509 tertiary alcohols Chemical class 0.000 claims abstract description 9
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
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- 235000001014 amino acid Nutrition 0.000 claims description 13
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
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- 239000003960 organic solvent Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- BMYNFMYTOJXKLE-UHFFFAOYSA-N DL-isoserine Natural products NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 6
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 6
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960003067 cystine Drugs 0.000 claims description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 6
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004158 L-cystine Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 5
- ZYJPUMXJBDHSIF-LLVKDONJSA-N (2r)-2-[(2-methylpropan-2-yl)oxycarbonylamino]-3-phenylpropanoic acid Chemical compound CC(C)(C)OC(=O)N[C@@H](C(O)=O)CC1=CC=CC=C1 ZYJPUMXJBDHSIF-LLVKDONJSA-N 0.000 claims description 4
- ZQEBQGAAWMOMAI-ZETCQYMHSA-N (2s)-1-[(2-methylpropan-2-yl)oxycarbonyl]pyrrolidine-2-carboxylic acid Chemical compound CC(C)(C)OC(=O)N1CCC[C@H]1C(O)=O ZQEBQGAAWMOMAI-ZETCQYMHSA-N 0.000 claims description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 4
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- OYXZPXVCRAAKCM-SANMLTNESA-N (2s)-2-[(2-methylpropan-2-yl)oxycarbonylamino]-3-(1-tritylimidazol-4-yl)propanoic acid Chemical compound C1=NC(C[C@H](NC(=O)OC(C)(C)C)C(O)=O)=CN1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 OYXZPXVCRAAKCM-SANMLTNESA-N 0.000 claims description 3
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- MIINHRNQLVVCEW-UHFFFAOYSA-N 132-16-1 Chemical compound [Fe+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MIINHRNQLVVCEW-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- VRPJIFMKZZEXLR-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxycarbonylamino]acetic acid Chemical compound CC(C)(C)OC(=O)NCC(O)=O VRPJIFMKZZEXLR-UHFFFAOYSA-N 0.000 claims description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- ONIBWKKTOPOVIA-SCSAIBSYSA-N D-Proline Chemical compound OC(=O)[C@H]1CCCN1 ONIBWKKTOPOVIA-SCSAIBSYSA-N 0.000 claims description 3
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- ODKSFYDXXFIFQN-SCSAIBSYSA-N D-arginine Chemical compound OC(=O)[C@H](N)CCCNC(N)=N ODKSFYDXXFIFQN-SCSAIBSYSA-N 0.000 claims description 3
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- 229930182820 D-proline Natural products 0.000 claims description 3
- KZSNJWFQEVHDMF-SCSAIBSYSA-N D-valine Chemical compound CC(C)[C@@H](N)C(O)=O KZSNJWFQEVHDMF-SCSAIBSYSA-N 0.000 claims description 3
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- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 3
- ZTVZLYBCZNMWCF-WDSKDSINSA-N L,L-homocystine zwitterion Chemical compound OC(=O)[C@@H](N)CCSSCC[C@H](N)C(O)=O ZTVZLYBCZNMWCF-WDSKDSINSA-N 0.000 claims description 3
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 claims description 3
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 3
- 229930182821 L-proline Natural products 0.000 claims description 3
- MDXGYYOJGPFFJL-QMMMGPOBSA-N N(alpha)-t-butoxycarbonyl-L-leucine Chemical compound CC(C)C[C@@H](C(O)=O)NC(=O)OC(C)(C)C MDXGYYOJGPFFJL-QMMMGPOBSA-N 0.000 claims description 3
- 239000012425 OXONE® Substances 0.000 claims description 3
- 239000004473 Threonine Substances 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- 235000003704 aspartic acid Nutrition 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 3
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 3
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 claims description 3
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 3
- 229940046149 ferrous bromide Drugs 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 229940076136 ferrous iodide Drugs 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 229960002885 histidine Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- BQZFDPZOAJMUIU-UHFFFAOYSA-N iron(3+);hexacyanide Chemical compound [Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BQZFDPZOAJMUIU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 3
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 claims description 3
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- 229960002429 proline Drugs 0.000 claims description 3
- 229960001153 serine Drugs 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229960002898 threonine Drugs 0.000 claims description 3
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 3
- XPEMYYBBHOILIJ-UHFFFAOYSA-N trimethyl(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](C)(C)C XPEMYYBBHOILIJ-UHFFFAOYSA-N 0.000 claims description 3
- 229960004441 tyrosine Drugs 0.000 claims description 3
- AQTUACKQXJNHFQ-LURJTMIESA-N (2s)-2-[(2-methylpropan-2-yl)oxycarbonylamino]pentanedioic acid Chemical compound CC(C)(C)OC(=O)N[C@H](C(O)=O)CCC(O)=O AQTUACKQXJNHFQ-LURJTMIESA-N 0.000 claims description 2
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 2
- QDGAVODICPCDMU-UHFFFAOYSA-N 2-amino-3-[3-[bis(2-chloroethyl)amino]phenyl]propanoic acid Chemical compound OC(=O)C(N)CC1=CC=CC(N(CCCl)CCCl)=C1 QDGAVODICPCDMU-UHFFFAOYSA-N 0.000 claims description 2
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 claims description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明公开了一种铁催化氧化环叔醇开环丙烯酸酯化的方法,该方法包括如下步骤:在溶剂中,以(E)‑3‑苯磺酰基丙烯酸甲酯为试剂,1‑芳基环叔醇为开环底物、过氧化物为氧化剂,铁为催化剂、氨基酸及其衍生物为配体,催化氧化环叔醇的C‑C单键断裂开环丙烯酸酯化反应,生成远端丙烯酸酯类化合物。本发明方法具有催化剂来源广泛、廉价和环保的优势;氧化剂来源广泛、廉价;反应条件温和、选择性高;非张力的环叔醇反应好;底物官能团相容性好且底物的适用范围广;实现高效远端官能团化策略来合成丙烯酸酯类化合物。在优化的反应条件之下,目标产品分离后产率可以达到82%。
Description
技术领域
本发明属于催化合成技术和精细化学品合成领域,涉及一种铁催化氧化环叔醇开环丙烯酸酯化的方法。
背景技术
碳-碳(C-C)σ键构成了有机分子的基本骨架。碳碳键的直接功能化是合成化学中最有效和最经济的转变之一。碳-碳(C-C)键的裂解与重组是工业上原油炼制的一项重要技术,温和反应条件下的可控选择性C-C键裂解在精细化工生产和实验室新反应创新中具有特殊用途。在过去的几十年里,过渡金属介导的碳碳键活化得到了快速发展。相比之下,自由基促进的C-C键裂解受到的关注相对较少。作为过渡金属催化的补充,可控自由基反应成为激活C-C键的有力工具。环叔醇是合成远端取代烷基酮和多环芳烃(PAHs)的有利前体。采用开环策略,环叔醇直接功能化能够形成C-C键。由于环应变的发生显著促进了环C-C键的裂变,张力能释放驱动的C-C键的活化主要依赖于三元环和四元环。非张力分子C-C键官能团化(如5-6元环)仍然是具有挑战性的。因此,非张力环C-C键的活化具有重要的意义。
在目前的环叔醇开环反应中仍然存在一些挑战,例如反应条件苛刻、官能团耐受性差导致底物的局限性(X.Wu,C.Zhu*,Chin.J.Chem.,2019,37,171-182.)、采用贵金属催化、溶剂毒性大、原子经济性差(X.Wu,C.Zhu*,Chin.J.Chem.,2019,37,171-182.)、仅适用于张力环叔醇的氧化开环、氧化剂DMP(戴斯-马丁高碘烷)制备困难、价格昂贵(X.Wu,C.Zhu*Chem.Rec.,2018,18,587-598.),这些都严重限制了该方法的大规模应用。
发明内容
发明目的:针对现有技术存在的问题,本发明提供一种铁催化氧化环叔醇开环丙烯酸酯化的方法,是铁催化合适的氧化剂氧化环叔醇实现环叔醇开环合成远端丙烯酸酯类化合物的方法。本发明的方法不仅为丙烯酸酯类化合物的合成提供一种经济和适用的新方法,而且解决现有非张力环叔醇开环反应存在的一系列问题,如反应件苛刻、反应产率低、需要使用贵金属催化剂等的问题。
本发明的方法只需要一步反应,不需要酸碱参与,同时具有催化剂来源广泛、廉价和环保的特点;氧化剂廉价和毒性低;底物来源广泛和稳定;反应条件温和,选择性好;底物官能团相容性好且底物的适用范围广;张力环叔醇和非张力环叔醇皆可兼容,能很好的实现非张力环叔醇开环合成远端官能团化的丙烯酸酯类化合物。
技术方案:为了实现上述目的,本发明所述一种铁催化氧化环叔醇开环丙烯酸酯化的方法,包括如下步骤:在溶剂中,以(E)-3-苯磺酰基丙烯酸甲酯为试剂,1-芳基环叔醇为开环底物、过氧化物为氧化剂,铁为催化剂、氨基酸或其衍生物为配体,催化氧化环叔醇的C-C单键断裂开环丙烯酸酯化反应,生成远端官能团化的丙烯酸酯类化合物;
反应通式表示如下:
式中:R1表示烷基或者卤素;R2表示烷基;n=3,4,5,6,7;m=1,2,3,4,5。
其中,以R1表示环叔醇中芳基上的取代基,R1单取代芳环上的氢,R1为烷基或者卤素。
其中,所述R1表示的烷基为甲基、乙基、异丙基或者叔丁基;R2表示的烷基为甲基或者正戊基。
作为优选,所述烷基一般为甲基。
其中,所述铁选自三氟甲磺酸亚铁、三氟甲磺酸铁、氯化亚铁、乙酰丙酮亚铁、乙酰丙酮铁、2,2,6,6-四甲基-3,5-庚二酮亚铁、2,2,6,6-四甲基-3,5-庚二酮铁、1,3-二苯基丙二酮亚铁、1,3-二苯基丙二酮铁、苯甲酰丙酮亚铁、苯甲酰丙酮铁、铁氰化亚铁、铁氰化铁、醋酸亚铁、硫酸亚铁、硫酸亚铁铵、硫酸铁、草酸亚铁、草酸铁、氟化亚铁、氟化铁、溴化亚铁、溴化铁、碘化亚铁、碘化铁、三氯化铁、高氯酸铁(III)水合物、1,1'-双(二苯基膦)二茂铁、酞菁亚铁、硝酸铁、氧化铁或四氧化三铁。
其中,所述配体选自S-乙酰胺基甲基-N-叔丁氧羰基-L-半胱氨酸、N-乙酰-L-半胱氨酸、N,N'-双(叔丁氧羰基)-L-胱氨酸、L-丝氨酸、D-胱氨酸、天冬氨酸、D-精氨酸、异丝氨酸、L-苏氨酸、L-酪氨酸、BOC-L-脯氨酸、BOC-甘氨酸-甘氨酸-甘氨酸、2-烯丙基-N-FMOC-L-甘氨酸、BOC-D-苯丙氨酸、L-半胱氨酸、D-丝氨酸、β-硫基缬氨酸、D-脯氨酸、D-缬氨酸、L-脯氨酸、L-苯丙氨酸、N-BOC-N'-三苯甲基-L-组氨酸、L-色氨酸、N-BOC-L-亮氨酸、L-组氨酸、BOC-L-谷氨酸、L-胱氨酸或者L-高胱氨酸。
其中,所述氧化剂选自过硫酸钾、过硫酸铵、过硫酸钠、叔丁基过氧化氢、过氧化氢、过氧乙酸、间氯过氧苯甲酸、过氧化苯甲酰、过氧化苯甲酰叔丁酯、二叔丁基过氧化物、单过硫酸氢钾、过氧化二异丙苯、2-过氧化丁酮或者双(三甲基硅基)过氧化物。
其中,所述溶剂为有机溶剂、水或有机溶剂的水溶液,所述有机溶剂选自甲醇、乙醇、乙二醇、正丙醇、异丙醇、1,3-丙二醇、甘油、正丁醇、异丁醇、叔丁醇、三氟乙醇、2-甲基-2-丁醇、3-甲氧基丁醇、仲丁醇、叔戊醇、4-甲基-2-戊醇、异戊醇、2-戊醇、3-戊醇、环戊醇、正戊醇、聚乙二醇200-10000、乙腈、苯腈、甲苯、丙酮、二氯甲烷、1,2-二氯乙烷、二甲亚砜、N,N-二甲酰胺、N,N-二乙酰胺、乙酸乙酯、1,4-二氧六环或四氢呋喃;所述溶剂为有机溶剂的水溶液时,所述有机溶剂与水的体积比为1:(0.1~5)。
其中,所述所述(E)-3-苯磺酰基丙烯酸甲酯试剂、1-芳基环叔醇、过氧化物、氨基酸或其衍生物、铁催化剂的摩尔比为1:(2~50):(2~50):(0.002~20):(0.001~10)。
其中,所述反应的温度为25~150℃、时间为0.25~48小时。
本发明的方法中铁的催化剂具有天然丰度大、价格低廉和毒性很小的特点,使用了特定氨基酸类配体,与铁催化剂进行配位,形成了高活性催化物种,这种催化物种和氧化剂、溶剂等共同作用,使环叔醇形成烷基自由基进攻(E)-3-苯磺酰基丙烯酸甲酯试剂,具有高的活性和选择性。此外,本发明的方法中使用温和的试剂,温和的环境,解决了反应条件苛刻的问题;解决了非张力环开环困难的问题;反应直接进攻(E)-3-苯磺酰基丙烯酸甲酯试剂,无需预官能团化,铁为催化剂,不用贵金属,并且效果显著。本发明方法具有催化剂来源广泛、廉价和环保的优势;氧化剂来源广泛、廉价;反应条件温和、选择性高;非张力的环叔醇反应好;底物官能团相容性好且底物的适用范围广;实现高效远端官能团化策略来合成丙烯酸酯类化合物。在优化的反应条件之下,目标产品分离后产率可以达到82%。
本发明首先通过氧化剂将低价铁氧化成高价铁,并且生成相应的阴离子自由基。然后阴离子自由基夺取1-芳基环叔醇的氢离子,提供烷氧自由基。通过C-C键断裂生成烷基自由基。烷基自由基与(E)-3-苯磺酰基丙烯酸甲酯相互作用生成远端官能团化的丙烯酸酯类化合物。最后,苯磺酰基自由基失去电子得到苯磺酰基阳离子,而高价铁得到电子又转化为低价铁,由此完成催化循环。本发明通过引入氨基酸或其衍生物,与铁催化剂进行配位。通过实践,证明取得了良好的效果。通过引入氨基酸或其衍生物,与铁催化剂进行配位,形成了高活性催化物种,从而解决现有仅适用于张力环叔醇的氧化开环,官能团耐受性差导致底物的局限性的问题。
有益效果:与现有技术相比,本发明具有如下优点:
(1)本发明提供了一种氨基酸及其衍生物类配体促进的铁催化氧化环叔醇开环丙烯酸酯化的方法,该方法只需一步反应,无需酸或碱的参与,且具有催化剂、配体和氧化剂廉价、来源广泛和环保的独特优势;反应条件温和,且选择性高;底物来源广泛、稳定和易于处理;底物官能团相容性好且底物的适用范围广;实验结果证明反应适用于非张力环叔醇的优势,而现有技术中并未有好的方法形成高活性的催化剂物种;
(2)本发明提供的环叔醇开环丙烯酸酯化的方法简单易行和安全,一步法直接得到远端官能团化的丙烯酸酯类化合物,在优化的反应条件之下,目标产品分离后产率可以达到82%,是一种通用、高效、经济和环境友好的环叔醇开环丙烯酸酯化的方法;
(3)本发明的方法之所以能够使用理想的铁为催化剂进行反应,关键在于使用了氨基酸类配体,与铁催化剂进行配位,形成了高活性催化物种,使反应能够在非常温和的条件下进行环叔醇开环丙烯酸酯化反应,特别是对非张力环(特别是5-7元环)的底物也能取得理想的催化效果。
(4)本发明的方法合成的远端羰基丙烯酸酯类化合物可以作为药物或生物活性分子,同时是重要的有机中间体,广泛应用于医药中间体和高附加值精细化学品的合成。
具体实施方式
根据下述实施例,可以更好地理解本发明。然而,本领域的技术人员容易理解,实施例所描述的内容仅用于说明本发明,而不应当也不会限制权利要求书中所详细描述的本发明。
实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径或通过下面方法简单制备获得。
实施例中的底物和产物的具体结构见表1。
其中底物1a为:(E)-3-苯磺酰基丙烯酸甲酯(合成可参考下文献的中化合物5c:Stereoselective synthesis of substituted arylsulfonylated 1,3-butadienesand2-propenoates by sulfonylation of acetylenic ester,Journal of SulfurChemistry,2013,Vol.34,No.5,532–538)。
2b-2be的合成方法:
其中,所述R3表示烷基或者卤素,烷基为甲基、乙基、异丙基或者叔丁基;R4表示的烷基为甲基或者正戊基。n=1,2,3,4,上述结构与表1中原料对应。
氮气中,在25mL反应瓶中依次加入镁,无水氯化锂,然后滴加芳基溴。加芳基溴后,需要用吹风机加热引发(时间大概持续5min),加热到四氢呋喃(THF)回流或者反应液产生气泡,并且反应瓶放出大量的热即停止加热,在室温下反应至温度降至室温,并观察到镁屑基本被消耗完再加入相应的酮。然后在室温下反应2h,TLC检测观察到荧光较弱并拖尾的点(PE:EA from 40:1to 20:1)。反应溶液搅拌2h,加入饱和氯化铵溶液(4mL)猝灭。进一步搅拌后用乙酸乙酯(3×20mL)萃取。
氮气中,在25mL反应瓶中依次加入镁,无水氯化锂,然后滴加溴苯。加溴苯后,需要用吹风机加热引发(时间大概持续5min),加热到四氢呋喃(THF)回流或者反应液产生气泡,并且反应瓶放出大量的热即停止加热,在室温下反应至温度降至室温,并观察到镁屑基本被消耗完再加入三环【5,2,1,0(2,6)】癸-8-酮。然后在室温下反应2h,TLC检测观察到荧光较弱并拖尾的点(PE:EA from 40:1to 20:1)。反应溶液搅拌2h,加入饱和氯化铵溶液(4mL)猝灭。进一步搅拌后用乙酸乙酯(3×20mL)萃取。
氮气中,在25mL反应瓶中依次加入镁,无水氯化锂,然后滴加溴苯。加溴苯后,需要用吹风机加热引发(时间大概持续5min),加热到四氢呋喃(THF)回流或者反应液产生气泡,并且反应瓶放出大量的热即停止加热,在室温下反应至温度降至室温,并观察到镁屑基本被消耗完再加入1-四氢萘酮。然后在室温下反应2h,TLC检测观察到荧光较弱并拖尾的点(PE:EA from 40:1to 20:1)。反应溶液搅拌2h,加入饱和氯化铵溶液(4mL)猝灭。进一步搅拌后用乙酸乙酯(3×20mL)萃取。
氮气中,在25mL反应瓶中加入2-3mL四氢呋喃。在5min之内将含四氢呋喃的6mmolMeMgBr(3M)加入到含四氢呋喃的4mmol钛酸异丙酯中。溶液变黄,冷却到0℃,然后加入4mmol苯甲酸甲酯。0℃下,反应30-40min后,加入6mmol EtMgBr(1M),加热至室温,搅拌1h。反应结束后,反应液在0℃下加入16mL 10%H2SO4稀释,然后用乙酸乙酯(3×20mL)萃取。
实施例1
化合物1的合成
氮气中,25mL反应瓶中依次加入三氟甲磺酸铁(0.05mmol),L-胱氨酸(0.2mmol),底物1a(0.5mmol),乙醇(2.0mL),底物2b(1mmol)和过硫酸钠(4mmol)。室温下混合均匀后,反应混合物在70℃下回流反应3h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=20:1)得到产物1,其产率79%。
实施例2
化合物2的合成
空气中,25mL反应瓶中依次加入乙酰丙酮铁(0.15mmol),S-乙酰胺基甲基-N-叔丁氧羰基-L-半胱氨酸(0.2mmol),底物1a(0.5mmol),异丙醇(2.0mL),底物2c(1.5mmol)和过氧乙酸(2mmol)。室温下混合均匀后,反应混合物在80℃下回流反应3h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=10:1)得到产物2,其产率72%。
实施例3
化合物3的合成
空气中,25mL反应瓶中依次加入乙酰丙酮亚铁(0.02mmol),L-苯丙氨酸(0.32mmol),底物1a(0.5mmol),叔丁醇(2.0mL),底物2d(3mmol)和二叔丁基过氧化物(1mmol)。室温下混合均匀后,反应混合物在25℃下回流反应3h。反应结束,直接层析分离(石油醚:二氯甲烷V/V=10:2)得到产物3,其产率71%。
1H NMR(400MHz,CDCl3):δ7.73(d,J=7.8Hz,1H),7.63(ddd,J=9.5,2.3,1.7Hz,1H),7.44(td,J=8.0,5.6Hz,1H),7.28-7.23(m,1H),6.96(dt,J=15.5,7.0Hz,1H),5.82(d,J=15.6Hz,1H),3.72(s,3H),2.94(t,J=7.3Hz,2H),2.22(ddd,J=14.5,7.3,1.3Hz,2H),1.78-1.71(m,2H),1.55-1.48(m,2H),1.44-1.37ppm(m,2H);13C NMR(100MHz,CDCl3):δ198.9(d,J=2Hz,1C),167.1,162.8(d,J=248Hz,1C),149.3,139.0(d,J=6Hz,1C),130.2(d,J=8Hz,1C),123.7(d,J=3Hz,1C),121.0,120.0(d,J=22Hz,1C),114.7(d,J=22Hz,1C),51.4,38.5,32.0,28.7,27.8,23.8ppm;19F NMR(300MHz,CDCl3):δ-111.9ppm;HRMS(ESI)calcd.for C16H19FO3H+[M+H+]m/z 279.1391,found 279.1382;IR(KBr,cm-1):νmax3359,2927,2854,1725,1689,1657,1590,1484,1441,1269,1246,1201,1174,1039,981,876,789,682.
实施例4
化合物4的合成
空气中,25mL反应瓶中依次加入醋酸亚铁(0.005mmol),L-脯氨酸(1.0mmol),底物1a(0.5mmol),正丁醇(1.5mL)和水(2.5mL),底物2e(2mmol)和过氧化氢(2.5mmol)。室温下混合均匀后,反应混合物在80℃下反应12h。反应结束,加入水5mL,并用乙酸乙酯萃取(5mL×3),合并有机相,减压蒸除溶剂后柱层析分离(石油醚:二氯甲烷V/V=40:1)得到产物4,其产率65%。
1H NMR(400MHz,CDCl3):δ7.98(dd,J=8.8,5.5Hz,2H),7.13(t,J=8.6Hz,2H),6.96(dt,J=15.5,7.0Hz,1H),5.82(d,J=15.6Hz,1H),3.72(s,3H),2.94(t,J=7.3Hz,2H),2.22(dd,J=13.7,6.6Hz,2H),1.78-1.70(m,2H),1.55-1.48(m,2H),1.44-1.37ppm(m,2H);13C NMR(100MHz,CDCl3):δ198.6,167.1,165.6(d,J=253Hz,1C),149.3,133.4(d,J=3Hz,1C),130.6(d,J=9Hz,1C),121.0,115.6(d,J=22Hz,1C),51.4,38.3,32.0,28.8,27.8,23.9ppm;19F NMR(300MHz,CDCl3):δ-105.6ppm;HRMS(ESI)calcd.for C16H19FO3H+[M+H+]m/z 279.1391,found 279.1381;IR(KBr,cm-1):νmax 3353,2923,2852,1723,1684,1597,1506,1437,1411,1270,1231,1200,1156,981,843.
实施例5
化合物5的合成
空气中,25mL反应瓶中依次加入溴化铁(0.1mmol),异丝氨酸(0.3mmol),底物1a(0.5mmol),丙酮(1.5mL)和水(0.5mL),底物2f(1.5mmol)和叔丁基过氧化氢(2mmol)。室温下混合均匀后,反应混合物在100℃下反应2h。反应结束,加入水5mL,并用乙醚萃取(5mL×3),合并有机相,减压蒸除溶剂后柱层析分离(石油醚:乙酸乙酯V/V=20:1)得到产物5,其产率68%。
实施例6
化合物6的合成
空气中,25mL反应瓶中依次加入三氯化铁(0.08mmol),L-苏氨酸(0.4mmol),底物1a(0.5mmol),正戊醇(2.0mL),2g(1mmol)和叔丁基过氧化氢(1.5mmol)。室温下混合均匀后,反应混合物在60℃下反应3h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=40:1)得到产物6,其产率65%。
实施例7
化合物7的合成
常压氮气中,25mL反应瓶中依次加入硝酸铁(0.5mmol),L-酪氨酸(0.18mmol),底物1a(0.5mmol),乙腈(2.0mL),底物2h(1.5mmol)和间氯过氧苯甲酸(2mmol)。室温下混合均匀后,反应混合物在25℃下反应24h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=40:3)得到产物7,其产率79%。
实施例8
化合物8的合成
空气中,25mL反应瓶中依次加入氟化铁(0.05mmol),β-硫基缬氨酸(0.04mmol),底物1a(0.5mmol),乙腈(1.5mL)和水(1.5mL),底物2i(1mmol)和单过硫酸氢钾(1.5mmol)。室温下混合均匀后,反应混合物在80℃下反应5h。反应结束,加入水5mL,并用乙酸乙酯萃取(5mL×3),合并有机相,减压蒸除溶剂后柱层析分离(石油醚:乙酸乙酯V/V=20:3)得到产物8,其产率65%。
实施例9
化合物9的合成
空气中,25mL反应瓶中依次加入苯甲酰丙酮亚铁(0.2mmol),N-乙酰-L-半胱氨酸(0.02mmol),底物1a(0.5mmol),二氯甲烷(2.0mL),底物2j(3.5mmol)和过氧化苯甲酰(2.5mmol)。室温下混合均匀后,反应混合物在70℃下反应2h。反应结束,直接层析分离(石油醚:二氯甲烷V/V=10:1)得到产物9,其产率71%。
实施例10
化合物10的合成
常压氮气中,25mL反应瓶中依次加入溴化亚铁(0.1mmol),D-脯氨酸(0.3mmol),底物1a(0.5mmol),N,N-二甲酰胺(1.5mL)和水(0.5mL),底物2k(2mmol)和过硫酸钠(2mmol)。室温下混合均匀后,反应混合物在80℃下反应8h。反应结束,加入水5mL,并用乙酸乙酯萃取(5mL×3),合并有机相,用水洗涤(5mL×3),收集有机相,减压蒸除溶剂后柱层析分离(石油醚:乙醚V/V=20:3)得到产物10,其产率66%。
1H NMR(400MHz,CDCl3):δ7.95(d,J=7.2Hz,0.6H),7.81(d,J=8.6Hz,1.4H),7.60(d,J=8.6Hz,1.4H),7.46(t,J=7.6Hz,0.6H),6.99-6.92(m,1H),5.82(d,J=15.6Hz,1H),3.72(s,3H),2.97(t,J=7.3Hz,1H),2.93(t,J=7.3Hz,1H),2.22(dd,J=14.3,7.1Hz,2H),1.77-1.70(m,2H),1.55-1.47(m,2H),1.43-1.37ppm(m,2H);13C NMR(100MHz,CDCl3):δ199.1,167.1,149.3,131.9,129.5,128.6,128.0,121.0,51.4,38.3,32.0,28.7,27.8,23.8ppm;HRMS(ESI)calcd.for C16H19BrO3H+[M+H+]m/z 339.0591,found 339.0586;IR(KBr,cm-1):νmax 3357,2927,2853,1722,1686,1659,1586,1435,1270,1200,1176,1071,1038,1009,981,814,736,701.
实施例11
化合物11的合成
常压氮气中,25mL反应瓶中依次加入碘化铁(0.05mmol),天冬氨酸(0.1mmol),底物1a(0.5mmol),1,3-丙二醇(4.0mL),底物2l(1mmol)和过硫酸钾(1mmol)。室温下混合均匀后,反应混合物在25℃℃下反应48h。反应结束,加入水5mL,并用乙酸乙酯萃取(5mL×3),合并有机相,用水洗涤(5mL×3),收集有机相,减压蒸除溶剂后柱层析分离(石油醚:乙醚V/V=10:1)得到产物11,其产率78%。
1H NMR(400MHz,CDCl3):δ7.60(d,J=7.6Hz,1H),7.36(t,J=6.8Hz,1H),7.25(t,J=7.5Hz,2H),6.96(dt,J=15.6,7.0Hz,1H),5.82(dt,J=15.6,1.5Hz,1H),3.72(s,3H),2.88(t,J=7.3Hz,2H),2.48(s,3H),2.24-2.19(m,2H),1.75-1.68(m,2H),1.54-1.47(m,2H),1.42-1.35ppm(m,2H);13C NMR(100MHz,CDCl3):δ204.5,167.1,149.4,138.1,137.8,131.9,131.1,128.2,125.6,121.0,51.4,41.4,32.0,28.7,27.8,24.1,21.2ppm;HRMS(ESI)calcd.for C17H22O3H+[M+H+]m/z275.1642,found 275.1633;IR(KBr,cm-1):νmax 3359,3190,2924,2853,1723,1684,1602,1435,1270,1198,1039,980,857,735.
实施例12
化合物12的合成
空气中,25mL反应瓶中依次加入氟化亚铁(0.02mmol),BOC-甘氨酸-甘氨酸-甘氨酸(0.2mmol),底物1a(0.5mmol),二氯甲烷(2.0mL),底物2m(1mmol)和2-过氧化丁酮(1.5mmol)。室温下混合均匀后,反应混合物在25℃下反应12h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=10:3)得到产物12,其产率82%。
1H NMR(400MHz,CDCl3):δ7.76-7.73(m,2H),7.38-7.26(m,2H),7.00-6.93(m,1H),5.82(d,J=15.6Hz,1H),3.72(s,3H),2.95(t,J=7.3Hz,2H),2.41(s,3H),2.22(dd,J=13.9,7.0Hz,2H),1.78-1.70(m,2H),1.55-1.48(m,2H),1.44-1.37ppm(m,2H);13C NMR(100MHz,CDCl3):δ200.5,167.1,149.4,138.3,137.0,133.7,128.5,128.4,125.2,121.0,51.4,38.4,32.0,28.8,27.9,24.0,21.4ppm;HRMS(ESI)calcd.for C17H22O3H+[M+H+]m/z275.1642,found 275.1631;IR(KBr,cm-1):νmax 2930,2858,1727,1686,1460,1271,1124,1073,1040,743.
实施例13
化合物13的合成
空气中,25mL反应瓶中依次加入铁氰化亚铁(0.001mmol),L-丝氨酸(0.1mmol),底物1a(0.5mmol),二甲亚砜(2.0mL),底物2n(1mmol)和过氧化二异丙苯(3mmol)。室温下混合均匀后,反应混合物在50℃下反应3h。反应结束,直接层析分离(石油醚:乙醚V/V=10:7)得到产物13,其产率79%。
1H NMR(400MHz,CDCl3):δ7.85(d,J=8.1Hz,2H),7.25(d,J=7.5Hz,2H),6.96(dt,J=15.5,7.0Hz,1H),5.82(d,J=15.6Hz,1H),3.72(s,3H),2.94(t,J=7.3Hz,2H),2.41(s,3H),2.22(dd,J=13.6,6.6Hz,2H),1.77-1.70(m,2H),1.55-1.47(m,2H),1.44-1.36ppm(m,2H);13C NMR(100MHz,CDCl3):δ199.9,167.1,149.4,143.7,134.5,129.2,128.1,121.0,51.4,38.3,32.0,28.8,27.9,24.1,21.6ppm;HRMS(ESI)calcd.for C17H22O3H+[M+H+]m/z275.1642,found 275.1640;IR(KBr,cm-1):νmax 3359,2926,2854,1725,1683,1609,1435,1270,1180,1036,978,810,719.
实施例14
化合物14的合成
空气中,25mL反应瓶中依次加入铁氰化铁(0.05mmol),BOC-L-脯氨酸(0.002mmol),底物1a(0.5mmol),乙腈(1.0mL)和水(1.0mL),底物2o(1.5mmol)和过硫酸铵(1.5mmol)。室温下混合均匀后,反应混合物在60℃下反应2h。反应结束,加入水5mL,并用乙酸乙酯萃取(5mL×3),合并有机相,减压蒸除溶剂后柱层析分离(石油醚:乙酸乙酯V/V=20:1)得到产物14,其产率80%。
实施例15
化合物15的合成
常压氮气中,25mL反应瓶中依次加入酞菁亚铁(0.02mmol),L-组氨酸(0.15mmol),底物1a(0.5mmol),1,2-二氯乙烷(2.0mL),底物2p(2.5mmol)和过氧化苯甲酰叔丁酯(1.5mmol)。室温下混合均匀后,反应混合物在70℃下反应6h。反应结束,加入水5mL,并用乙酸乙酯萃取(5mL×3),合并有机相,减压蒸除溶剂后柱层析分离(石油醚:乙酸乙酯V/V=40:1)得到产物15,其产率69%。
实施例16
化合物16的合成
空气中,25mL反应瓶中依次加入三氟甲磺酸亚铁(0.05mmol),L-半胱氨酸(0.04mmol),底物1a(0.5mmol),乙酸乙酯(2.0mL),底物2q(1.5mmol)和过硫酸钾(1mmol)。室温下混合均匀后,反应混合物在90℃下反应3h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=40:7)得到产物16,其产率76%。
实施例17
化合物17的合成
空气中,25mL反应瓶中依次加入1,3-二苯基丙二酮铁(0.04mmol),BOC-D-苯丙氨酸(0.1mmol),底物1a(0.5mmol),N,N-二乙酰胺(2.0mL),底物2r(1.5mmol)和过氧化氢(1.5mmol),室温下混合均匀后,反应混合物在90℃下反应6h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=20:1)得到产物17,其产率62%。
实施例18
化合物18的合成
空气中,25mL反应瓶中依次加入草酸亚铁(0.1mmol),D-缬氨酸(0.15mmol),底物1a(0.5mmol),1,4-二氧六环(2.0mL),底物2s(1mmol)和过氧化氢(1mmol)。室温下混合均匀后,反应混合物在50℃下反应10h。反应结束,直接层析分离(石油醚:二氯甲烷V/V=10:3)得到产物18,其产率59%。
实施例19
化合物19的合成
空气中,25mL反应瓶中依次加入硫酸亚铁(0.05mmol),BOC-L-脯氨酸(0.1mmol),底物1a(0.5mmol),甲苯(2.0mL),底物2t(1.5mmol)和过硫酸钠(1.5mmol)。室温下混合均匀后,反应混合物在60℃下反应12h。反应结束,直接层析分离(石油醚:二氯甲烷V/V=10:5)得到产物19,其产率49%。
实施例20
化合物20的合成
空气中,25mL反应瓶中依次加入1,3-二苯基丙二酮亚铁(0.08mmol),BOC-L-谷氨酸(0.4mmol),底物1a(0.5mmol),四氢呋喃(1.0mL)和水(1.0mL),底物2u(2mmol)和间氯过氧苯甲酸(1mmol)。室温下混合均匀后,反应混合物在120℃下反应2h。反应结束,加入水5mL,并用乙醚萃取(5mL×3),合并有机相,减压蒸除溶剂后柱层析分离(石油醚:乙酸乙酯V/V=20:3)得到产物20,其产率69%。
1H NMR(400MHz,CDCl3):δ7.95(d,J=7.1Hz,2H),7.55(t,J=7.4Hz,2H),7.46(t,J=7.6Hz,2H),6.86(dd,J=15.7,8.0Hz,1H),5.78(dd,J=15.7,1.0Hz,1H),3.72(s,3H),2.96(t,J=7.3,2H),2.35-2.29(m,1H),1.76-1.68(m,2H),1.45-1.34(m,4H),1.05ppm(d,J=6.7Hz,3H);13C NMR(100MHz,CDCl3):δ200.2,167.3,154.7,137.0,133.0,128.5,128.0,119.3,51.4,38.4,36.4,35.8,26.9,24.2,19.4ppm;HRMS(ESI)calcd.for C17H22O3H+[M+H+]m/z 275.1642,found275.1631;IR(KBr,cm-1):νmax 3358,2928,2852,1722,1686,1657,1448,1435,1354,1274,1199,986,753,692.
实施例21
化合物21的合成
空气中,25mL反应瓶中依次加入氯化亚铁(0.05mmol),BOC-D-苯丙氨酸(0.03mmol),底物1a(0.5mmol),仲丁醇(2.0mL),底物2v(1mmol)和单过硫酸氢钾(2mmol)。室温下混合均匀后,反应混合物在50℃下反应24h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=20:1)得到产物21,其产率56%。
1H NMR(400MHz,CDCl3):δ7.95(d,J=7.3Hz,2H),7.56(t,J=7.3Hz,1H),7.46(t,J=7.6Hz,2H),6.97(dt,J=15.4,7.0Hz,1H),5.83(d,J=15.6Hz,1H),3.72(s,3H),3.00-2.94(m,2H),2.28-2.20(m,2H),1.84-1.77(m,1H),1.61-1.48(m,4H),0.95ppm(d,J=5.9Hz,3H);13C NMR(100MHz,CDCl3):δ200.5,167.1,149.6,136.9,133.0,128.6,128.0,120.9,51.4,36.1,35.0,32.1,30.9,29.7,19.2ppm;HRMS(ESI)calcd.for C17H22O3H+[M+H+]m/z 275.1642,found 275.1635;IR(KBr,cm-1):νmax 3353,2921,2851,1723,1685,1658,1449,1272,1211,1177,986,741,691.
实施例22
化合物22的合成
空气中,25mL反应瓶中依次加入硫酸亚铁铵(0.1mmol),N,N'-双(叔丁氧羰基)-L-胱氨酸(0.4mmol),底物1a(0.5mmol),乙二醇(2.0mL),底物2w(1.5mmol)和二叔丁基过氧化物(1mmol)。室温下混合均匀后,反应混合物在70℃下反应3h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=10:1)得到产物22,其产率68%。
1H NMR(400MHz,CDCl3):δ7.94(d,J=7.2Hz,2H),7.56(t,J=7.4Hz,1H),7.46(t,J=7.6Hz,2H),6.96(dt,J=15.6,6.9Hz,1H),5.81(d,J=15.6Hz,1H),3.72(s,3H),2.92(dd,J=16.1,5.9Hz,1.33H),2.78(dd,J=16.0,7.7Hz,0.67H),2.25-2.16(m,2H),1.82-1.74(m,0.67H),1.71-1.63(m,1.33H),1.55-1.47(m,1.5H),1.45-1.38(m,1.5H),0.96(d,J=6.7Hz,2H),0.93ppm(d,J=6.7Hz,1H);13C NMR(100MHz,CDCl3):δ200.1,167.1,149.4,137.3,132.9,128.6,128.0,121.0,51.4,45.8,36.5,32.3,29.5,25.5,19.9ppm;HRMS(ESI)calcd.for C17H22O3H+[M+H+]m/z 275.1642,found 275.1637;IR(KBr,cm-1):νmax 2925,1724,1686,1449,1437,1318,1272,1210,1179,1039,980,751,691.
实施例23
化合物23的合成
空气中,25mL反应瓶中依次加入高氯酸铁(III)水合物(0.05mmol),L-色氨酸(0.5mmol),底物1a(0.5mmol),甘油(2.0mL),底物2x(1.5mmol)和2-过氧化丁酮(1.5mmol)。室温下混合均匀后,反应混合物在110℃下反应2h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=20:1)得到产物23,其产率60%。
实施例24
化合物24的合成
空气中,25mL反应瓶中依次加入氧化铁(0.2mmol),L-高胱氨酸(0.1mmol),底物1a(0.5mmol),环戊醇(2.0mL),底物2y(1.5mmol)和2-过氧化丁酮(2mmol)。室温下混合均匀后,反应混合物在60℃下反应6h。反应结束,加入水5mL,并用乙酸乙酯萃取(5mL×3),合并有机相,用水洗涤(5mL×3),收集有机相,减压蒸除溶剂后柱层析分离(石油醚:二氯甲烷V/V=10:4)得到产物24,其产率65%。
1H NMR(400MHz,CDCl3):δ7.95(d,J=7.2Hz,2H),7.57(t,J=7.4Hz,1H),7.47(t,J=7.6Hz,2H),7.04(dt,J=15.6,6.8Hz,1H),5.90(d,J=15.7Hz,1H),3.72(s,3H),3.15(t,J=7.3Hz,2H),2.66ppm(qd,J=7.2,1.4Hz,2H);13C NMR(100MHz,CDCl3):δ198.1,166.9,147.7,136.5,133.3,128.7,127.9,121.7,51.5,36.6,26.3ppm;HRMS(ESI)calcd.forC13H14O3H+[M+H+]m/z 219.1016,found219.1009;IR(KBr,cm-1):νmax 3350,2950,2921,2850,1718,1683,1655,1447,1435,1373,1267,1010,971,863,744,701,688,568.
实施例25
化合物25的合成
空气中,25mL反应瓶中依次加入苯甲酰丙酮铁(0.05mmol),N-BOC-L-亮氨酸(0.1mmol),底物1a(0.5mmol),叔戊醇(1.5mL)和水(0.5mL),底物2z(1mmol)和过氧化氢(2mmol)。室温下混合均匀后,反应混合物在80℃下反应24h。反应结束,加入氨水(0.5mL,25%),并搅拌1h。紧接着,加入水5mL,并用乙醚萃取(5mL×3),合并有机相,减压蒸除溶剂后柱层析分离(石油醚:二氯甲烷V/V=10:3)得到产物25,其产率61%。
1H NMR(400MHz,CDCl3):δ7.94(d,J=7.1Hz,2H),7.56(t,J=7.4Hz,1H),7.46(t,J=7.6Hz,2H),6.98(dt,J=15.6,6.9Hz,1H),5.86(dt,J=15.7,1.5Hz,1H),3.72(s,3H),3.00(t,J=7.2Hz,2H),2.31(ddd,J=8.4,7.4,1.5Hz,2H),1.96-1.89ppm(m,2H);13C NMR(100MHz,CDCl3):δ199.5,166.9,148.5,136.8,133.1,128.6,127.9,121.6,51.4,37.4,31.5,22.3ppm;HRMS(ESI)calcd.for C14H16O3H+[M+H+]m/z 233.1172,found 233.1166;IR(KBr,cm-1):νmax 3504,2948,1723,1679,1597,1447,1321,1276,1202,1041,978,755,737,692,657,568.
实施例26
化合物26的合成
空气中,25mL反应瓶中依次加入草酸铁(0.05mmol),2-烯丙基-N-FMOC-L-甘氨酸(0.08mmol),底物1a(0.5mmol),叔戊醇(2.0mL),底物2ba(1mmol)和双(三甲基硅基)过氧化物(1mmol)。室温下混合均匀后,反应混合物在40℃下反应6h。反应结束,直接层析分离(石油醚:乙醚V/V=10:3)得到产物26,其产率71%。
1H NMR(400MHz,CDCl3):δ7.95(d,J=7.1Hz,2H),7.56(t,J=7.4Hz,1H),7.46(t,J=7.5Hz,2H),6.97(dt,J=15.6,7.0Hz,1H),5.84(dt,J=15.6,1.5Hz,1H),3.72(s,3H),2.99(t,J=7.2Hz,2H),2.27(ddd,J=14.7,7.3,1.5Hz,2H),1.82-1.74(m,2H),1.60-1.52ppm(m,2H);13C NMR(100MHz,CDCl3):δ199.9,167.1,149.0,136.9,133.0,128.6,128.0,121.2,51.4,38.2,32.1,27.7,23.7ppm;HRMS(ESI)calcd.for C15H18O3NH4 +[M+NH4 +]m/z 264.1594,found 264.1588;IR(KBr,cm-1):νmax 3357,2925,2852,1723,1687,1656,1449,1272,1200,1037,978,752,692.
实施例27
化合物27的合成
空气中,25mL反应瓶中依次加入2,2,6,6-四甲基-3,5-庚二酮亚铁(0.05mmol),D-丝氨酸(0.1mmol),底物1a(0.5mmol),异丁醇(1.5mL)和水(0.5mL),底物2bb(3mmol)和过硫酸铵(2mmol)。室温下混合均匀后,反应混合物在70℃下反应6h。反应结束,加入氨水(0.5mL,25%),并搅拌1h。紧接着,加入水5mL,并用乙酸乙酯萃取(5mL×3),合并有机相,减压蒸除溶剂后柱层析分离(石油醚:二氯甲烷V/V=10:5)得到产物27,其产率81%。
实施例28
化合物28的合成
空气中,25mL反应瓶中依次加入碘化亚铁(0.05mmol),D-精氨酸(0.1mmol),底物1a(0.5mmol),苯腈(2mL),底物2bc(1mmol)和二叔丁基过氧化物(3mmol)。室温下混合均匀后,反应混合物在80℃下反应4h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=20:1)得到产物28,其产率60%。
实施例29
化合物29的合成
空气中,25mL反应瓶中依次加入1,1'-双(二苯基膦)二茂铁(0.02mmol),L-胱氨酸(0.1mmol),底物1a(0.5mmol),N,N-二甲酰胺(1.5mL)和水(0.5mL),底物2bd(1mmol)和过硫酸钠(1.5mmol)。室温下混合均匀后,反应混合物在25℃下反应48h。反应结束,加入氨水(0.5mL,25%),并搅拌1h。紧接着,加入水5mL,并用乙酸乙酯萃取(5mL×3),合并有机相,减压蒸除溶剂后柱层析分离(石油醚:乙酸乙酯V/V=20:3)得到产物29,其产率46%,本实施例产率不高的原因可能是多了一个苄位,存在苄位氧化与开环过程的竞争。
1H NMR(400MHz,CDCl3):δ7.79(d,J=7.1Hz,2H),7.59(t,J=7.4Hz,1H),7.46(t,J=7.7Hz,2H),7.42(dd,J=7.3,1.4Hz,1H),7.35(d,J=4.3Hz,1H),7.32-7.28(m,2H),6.88(dt,J=15.6,6.9Hz,1H),5.76(dt,J=15.6,1.5Hz,1H),3.70(s,3H),2.68(t,J=7.7Hz,2H),2.16(dd,J=13.6,6.8Hz,2H),1.76-1.68ppm(m,2H);13C NMR(100MHz,CDCl3):δ198.6,167.0,148.9,140.8,138.4,137.8,133.2,130.3,130.2,130.1,128.7,128.4,125.4,121.2,51.4,32.8,31.8,29.9ppm;HRMS(ESI)calcd.for C20H20O3H+[M+H+]m/z 309.1485,found 309.1478;IR(KBr,cm-1):νmax 3358,2923,2851,1725,1662,1448,1270,1196,929,761,705,641.
实施例30
化合物30的合成
空气中,25mL反应瓶中依次加入2,2,6,6-四甲基-3,5-庚二酮铁(0.1mmol),N-BOC-N'-三苯甲基-L-组氨酸(0.2mmol),底物1a(0.5mmol),乙醇(2.0mL),底物2be(1mmol)和叔丁基过氧化氢(1mmol)。室温下混合均匀后,反应混合物在60℃下反应12h。反应结束,直接层析分离(石油醚:乙酸乙酯V/V=40:7)得到产物30,其产率62%。
实施例1~30的原料和产物结构式及对应的实验结果如下表1所示:
表1
实施例31
实施例31与实施例12的方法相同,不同之处在于:(E)-3-苯磺酰基丙烯酸甲酯试剂、环叔醇化合物、过氧化物、氨基酸衍生物、铁催化剂的摩尔比为1:2:2:0.002:0.001。
实施例32
实施例32与实施例12的方法相同,不同之处在于:(E)-3-苯磺酰基丙烯酸甲酯试剂、环叔醇化合物、过氧化物、氨基酸衍生物、铁催化剂的摩尔比为1:50:50:20:10。
实施例33
实施例33与实施例12的方法相同,不同之处在于:(E)-3-苯磺酰基丙烯酸甲酯试剂、环叔醇化合物、过氧化物、氨基酸衍生物、铁催化剂的摩尔比为1:30:30:20:10。
实施例34
实施例34与实施例12的方法相同,不同之处在于:溶剂全部为水,总体积保持不变。
对比例1
对比例1与实施例12的方法相同,不同之处在于:不加入铁催化剂,目标产物产率为0。
对比例2
对比例2与实施例12的方法相同,不同之处在于:不加入氨基酸类配体,反应产率大大降低,产率小于30%。
对比例3
对比例3与实施例12的方法相同,不同之处在于:不加入氧化剂,目标产物产率为0。
对比例4
对比例4与实施例12的方法相同,不同之处在于:采用非氨基酸类配体1,10-菲罗啉,产率仅为6%。此外,采用其他含磷的配体,如乙基二苯基膦、二乙基苯膦;或者含氮的配体,比如新铜试剂,其效果均不好,产率非常低。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,本发明中的各种铁催化剂理论上都能与氨基酸类配体配位形成高活性的铁催化剂物种,从而有利于反应的顺利进行;氨基酸类配体是发生环叔醇开环丙烯酸酯化反应的促进剂,利用的是其可与铁配位的效果,理论上给出的各种氨基酸及其衍生物都具有配位功能,都应能取得类似之效果;各种过氧化物是氧化剂;环叔醇上发生的是碳-碳键的活化,而芳香环上的各种取代基影响的是环内的电子云密度大小以及反应时的空间位阻大小,即取代基的修饰只是一定程度上影响反应,不对反应的发生起决定作用。任何熟悉本专业的技术人员不难理解,在不脱离本发明技术方案范围内,当可进行变动或修饰得到相应的实施例,例如对于所述的取代基可在本发明范围内进行替换、改变或修饰,均可以实现本发明方法。但凡是未脱离本发明技术方案的宗旨,依据本发明的对以上实施例所作的任何修改、修饰或等同与等效的变化,均仍属于本发明技术方案的范围内。
Claims (9)
2.根据权利要求1所述的铁催化氧化环叔醇开环丙烯酸酯化的方法,其特征在于,以R1表示环叔醇中芳基上的取代基,R1单取代芳环上的氢,R1为烷基或者卤素。
3.根据权利要求2所述的铁催化氧化环叔醇开环丙烯酸酯化的方法,其特征在于,所述R1表示烷基优选为甲基、乙基、异丙基或者叔丁基;R2表示的烷基优选为甲基或者正戊基。
4.根据权利要求1所述的铁催化氧化环叔醇开环丙烯酸酯化的方法,其特征在于,所述铁选自三氟甲磺酸亚铁、三氟甲磺酸铁、氯化亚铁、乙酰丙酮亚铁、乙酰丙酮铁、2,2,6,6-四甲基-3,5-庚二酮亚铁、2,2,6,6-四甲基-3,5-庚二酮铁、1,3-二苯基丙二酮亚铁、1,3-二苯基丙二酮铁、苯甲酰丙酮亚铁、苯甲酰丙酮铁、铁氰化亚铁、铁氰化铁、醋酸亚铁、硫酸亚铁、硫酸亚铁铵、硫酸铁、草酸亚铁、草酸铁、氟化亚铁、氟化铁、溴化亚铁、溴化铁、碘化亚铁、碘化铁、三氯化铁、高氯酸铁(III)水合物、1,1'-双(二苯基膦)二茂铁、酞菁亚铁、硝酸铁、氧化铁或四氧化三铁。
5.根据权利要求1所述的铁催化氧化环叔醇开环丙烯酸酯化的方法,其特征在于,所述配体选自S-乙酰胺基甲基-N-叔丁氧羰基-L-半胱氨酸、N-乙酰-L-半胱氨酸、N,N'-双(叔丁氧羰基)-L-胱氨酸、L-丝氨酸、D-胱氨酸、天冬氨酸、D-精氨酸、异丝氨酸、L-苏氨酸、L-酪氨酸、BOC-L-脯氨酸、BOC-甘氨酸-甘氨酸-甘氨酸、2-烯丙基-N-FMOC-L-甘氨酸、BOC-D-苯丙氨酸、L-半胱氨酸、D-丝氨酸、β-硫基缬氨酸、D-脯氨酸、D-缬氨酸、L-脯氨酸、L-苯丙氨酸、N-BOC-N'-三苯甲基-L-组氨酸、L-色氨酸、N-BOC-L-亮氨酸、L-组氨酸、BOC-L-谷氨酸、L-胱氨酸或者L-高胱氨酸。
6.根据权利要求1所述的铁催化氧化环叔醇开环丙烯酸酯化的方法,其特征在于,所述氧化剂选自过硫酸钾、过硫酸铵、过硫酸钠、叔丁基过氧化氢、过氧化氢、过氧乙酸、间氯过氧苯甲酸、过氧化苯甲酰、过氧化苯甲酰叔丁酯、二叔丁基过氧化物、单过硫酸氢钾、过氧化二异丙苯、2-过氧化丁酮或者双(三甲基硅基)过氧化物。
7.根据权利要求1所述的铁催化氧化环叔醇开环丙烯酸酯化的方法,其特征在于,所述溶剂为有机溶剂、水或有机溶剂的水溶液,所述有机溶剂选自甲醇、乙醇、乙二醇、正丙醇、异丙醇、1,3-丙二醇、甘油、正丁醇、异丁醇、叔丁醇、三氟乙醇、2-甲基-2-丁醇、3-甲氧基丁醇、仲丁醇、叔戊醇、4-甲基-2-戊醇、异戊醇、2-戊醇、3-戊醇、环戊醇、正戊醇、聚乙二醇200-10000、乙腈、苯腈、甲苯、丙酮、二氯甲烷、1,2-二氯乙烷、二甲亚砜、N,N-二甲酰胺、N,N-二乙酰胺、乙酸乙酯、1,4-二氧六环或四氢呋喃;所述溶剂为有机溶剂的水溶液时,所述有机溶剂与水的体积比为1:(0.1~5)。
8.根据权利要求1所述的铁催化氧化环叔醇开环丙烯酸酯化的方法,其特征在于,所述所述(E)-3-苯磺酰基丙烯酸甲酯试剂、1-芳基环叔醇、过氧化物、氨基酸或其衍生物、铁催化剂的摩尔比为1:(2~50):(2~50):(0.002~20):(0.001~10)。
9.根据权利要求1所述的铁催化氧化环叔醇开环丙烯酸酯化的方法,其特征在于,所述反应的温度为25~150℃、时间为0.25~48小时。
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