CN107868095B - 手性三价金络合物及其制备方法和应用 - Google Patents
手性三价金络合物及其制备方法和应用 Download PDFInfo
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- CN107868095B CN107868095B CN201610860285.5A CN201610860285A CN107868095B CN 107868095 B CN107868095 B CN 107868095B CN 201610860285 A CN201610860285 A CN 201610860285A CN 107868095 B CN107868095 B CN 107868095B
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- gold
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- chiral
- heteroaryl
- iii
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- 239000010931 gold Substances 0.000 title claims abstract description 93
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 91
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000010668 complexation reaction Methods 0.000 title description 2
- 239000003446 ligand Substances 0.000 claims abstract description 26
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims abstract description 11
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 claims abstract description 8
- GUWKQWHKSFBVAC-UHFFFAOYSA-N [C].[Au] Chemical compound [C].[Au] GUWKQWHKSFBVAC-UHFFFAOYSA-N 0.000 claims abstract description 8
- HGTYEBNTDPDGIC-UHFFFAOYSA-N [N].[Au] Chemical compound [N].[Au] HGTYEBNTDPDGIC-UHFFFAOYSA-N 0.000 claims abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003222 pyridines Chemical class 0.000 claims abstract description 8
- 230000003287 optical effect Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 125000001072 heteroaryl group Chemical group 0.000 claims description 41
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 40
- -1 2-substituted pyridine-gold (III) dichloride Chemical class 0.000 claims description 36
- 125000001424 substituent group Chemical group 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 125000002541 furyl group Chemical group 0.000 claims description 22
- 125000004076 pyridyl group Chemical group 0.000 claims description 22
- 125000001544 thienyl group Chemical group 0.000 claims description 22
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical class C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 claims description 21
- 238000007366 cycloisomerization reaction Methods 0.000 claims description 20
- 238000010523 cascade reaction Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 150000002367 halogens Chemical class 0.000 claims description 17
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 16
- 150000005691 triesters Chemical class 0.000 claims description 16
- NIYKZESDJZFCAC-UHFFFAOYSA-L [Au+](Cl)Cl.O1C=NCC1 Chemical compound [Au+](Cl)Cl.O1C=NCC1 NIYKZESDJZFCAC-UHFFFAOYSA-L 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 13
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- RLAHWVDQYNDAGG-UHFFFAOYSA-N Methanetriol Chemical compound OC(O)O RLAHWVDQYNDAGG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- SGJBIFUEFLWXJY-UHFFFAOYSA-N 1-(dibutoxymethoxy)butane Chemical compound CCCCOC(OCCCC)OCCCC SGJBIFUEFLWXJY-UHFFFAOYSA-N 0.000 claims description 4
- RWNXXQFJBALKAX-UHFFFAOYSA-N 1-(dipropoxymethoxy)propane Chemical compound CCCOC(OCCC)OCCC RWNXXQFJBALKAX-UHFFFAOYSA-N 0.000 claims description 4
- FPIVAWNGRDHRSQ-UHFFFAOYSA-N 2-[di(propan-2-yloxy)methoxy]propane Chemical compound CC(C)OC(OC(C)C)OC(C)C FPIVAWNGRDHRSQ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 239000001301 oxygen Substances 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
- 239000011593 sulfur Substances 0.000 claims description 4
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 5
- 125000000217 alkyl group Chemical group 0.000 claims 4
- 238000006317 isomerization reaction Methods 0.000 claims 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 218
- CBMIPXHVOVTTTL-UHFFFAOYSA-N gold(3+) Chemical class [Au+3] CBMIPXHVOVTTTL-UHFFFAOYSA-N 0.000 description 70
- 230000015572 biosynthetic process Effects 0.000 description 57
- 239000007787 solid Substances 0.000 description 57
- 238000003786 synthesis reaction Methods 0.000 description 57
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 53
- 238000005160 1H NMR spectroscopy Methods 0.000 description 53
- 239000003054 catalyst Substances 0.000 description 28
- 230000003197 catalytic effect Effects 0.000 description 24
- 239000000047 product Substances 0.000 description 17
- 238000006053 organic reaction Methods 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 10
- 239000003426 co-catalyst Substances 0.000 description 10
- 150000002343 gold Chemical class 0.000 description 9
- 238000007363 ring formation reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001976 improved effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000005968 oxazolinyl group Chemical group 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- SCXBFXGVOQYURB-UHFFFAOYSA-N 2-phenyl-1h-isoquinoline Chemical compound C1=CC2=CC=CC=C2CN1C1=CC=CC=C1 SCXBFXGVOQYURB-UHFFFAOYSA-N 0.000 description 2
- 101001110286 Homo sapiens Ras-related C3 botulinum toxin substrate 1 Proteins 0.000 description 2
- 102100022122 Ras-related C3 botulinum toxin substrate 1 Human genes 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 238000006664 bond formation reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 229920001184 polypeptide Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
- ZOSNTSSUDLIQGJ-UHFFFAOYSA-L Cl[Au](Cl)C1=CC=CC=C1 Chemical compound Cl[Au](Cl)C1=CC=CC=C1 ZOSNTSSUDLIQGJ-UHFFFAOYSA-L 0.000 description 1
- UCOBJOONLGFYMF-UHFFFAOYSA-L Cl[Au]Cl Chemical compound Cl[Au]Cl UCOBJOONLGFYMF-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZBKIUFWVEIBQRT-UHFFFAOYSA-N gold(1+) Chemical class [Au+] ZBKIUFWVEIBQRT-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000020046 sherry Nutrition 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- 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
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- 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
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/76—Benzo[c]pyrans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
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Abstract
本发明提供了一种手性三价金络合物，所述手性三价金络合物由两个碳‑金共价键、一个氧‑金共价键以及一个氮‑金配位键构成，具有手性联萘酚和噁唑啉配体骨架，或具有手性联萘酚和邻位取代吡啶配体骨架，所述手性三价金络合物具有下述通式I或通式II的化合物，以及所述通式I或通式II的消旋体和旋光异构体，
Description
技术领域
本发明属于有机化合物及合成技术领域，尤其涉及一种稳定的手性三价金络合物及其制备方法和应用。
背景技术
在过去的几十年中，有机金属催化剂的发展大多都以低价态过渡金属盐或络合物为研究对象。而对应的高价态过渡金属盐或络合物，由于反应活性太高以及其稳定络合物难以制备，在催化研究领域中未能得到广泛的发展。这一现象在金(Au)催化领域表现得尤为突出。近十年来，利用一价金络合物催化有机反应的研究吸引了越来越多化学家们的关注。迄今为止，有机化学家们已经发展了许多不同类型配体的金(I)络合物用于改善其稳定性、催化活性以及不对称诱导能力，并取得了很大的进展(W.Zi,F.D.Toste,Chem.Soc.Rev.2016,45,4567-4589；R.Dorel and A.M.Echavarren,Chem.Rev.2015,115,9028-9072；D.J.Gorin,B.D.Sherry,F.D.Toste,Chem.Rev.2008,108,3351–3378；A.S.K.Hashmi,M.Rudolph,Chem.Soc.Rev.2008,37,1766–1775；N.Marison,S.P.Nolan,Chem.Soc.Rev.2009,37,1776–1782)，使得金催化成为有机合成领域的一个热点。然而，多数三价金盐由于稳定性差，制备相应的络合物比较困难，以及在反应过程中催化活性太高，经常造成反应物的官能团兼容性差及产物选择性差等结果。因此，到目前为止，利用三价金盐或络合物作为催化剂用于催化有机反应的研究相对较少。
一般来说，有机配体的引入可以增加三价金的稳定性。然而，催化剂的稳定性的提高伴随着催化活性的降低，如果三价金络合物过于稳定又会造成其催化活性极低。因此，为了调控稳定性与催化活性两者的“平衡”，选用合适的有机配体或者加入活化试剂进行“激活”，在三价金催化剂的设计中非常关键。其中比较典型的例子有：2004年Hashmi发现了吡啶-2-甲酸是很好的三价金的配体，相应的络合物是个非常温和高效的催化剂(A.S.K.Hashmi,J.P.Weyrauch,M.Rudolph,E.
Angew.Chem.Int.Ed.2004,43,6545-6547)；2015年Toste课题组发现一种利用金(I)卡宾络合物与Biphenylene在温和的条件下通过氧化加成制备稳定的三价金络合物的方法，该金(III)络合物作为催化剂可以催化多种不同类型的反应(C.-Y.Wu,T.Horibe,C.B.Jacobsen,F.D.Toste,Nature 2015,517,449-454)。我们课题组近年来一直从事三价金络合物的合成及其在有机催化中的应用(V.K.-Y.Lo,Y.Liu,M.-K.Wong,C.-M.Che,Org.Lett.2006,8,1529-1532；V.K.-Y.Lo,K.K.-Y.Kung,M.-K.Wong,C.-M.Che,J.Organomet.Chem.2009,694,583-591；K.K.-Y.Kung,V.K.-Y.Lo,H.-M.Ko,G.-L.Li,P.-Y.Chan,K.-C.Leung,Z.Zhou,M.-Z.Wang,C.-M.Che,M.-K.Wong,Adv.Synth.Catal.2013,355,2055-2070；H.-M.Ko,K.K.-Y.Kung,J.-F.Cui,M.-K.Wong,Chem.Commun.2013,49,8869-8871)。我们发现：金原子中心带一个正电荷的双配体的双(2-苯基喹啉)基一氯化金和双(2-苯基异喹啉)基一氯化金，比金原子中心带两个正电荷的单配体的(2-苯基喹啉)基二氯化金和(2-苯基异喹啉)基一氯化金分别要稳定得多，催化活性也有所下降，但可以加入银盐来“激活”其催化活性来获得我们希望的催化效果(H.-M.Ko,K.K.-Y.Kung,J.-F.Cui,M.-K.Wong,Chem.Commun.2013,49,8869-8871)。因此，发展一些易于合成的、稳定性与反应活性可以保持“平衡”的稳定三价金络合物，将对拓展金催化有机反应的研究具有重要的意义。
另外，由于一价金离子直线性双配位的性质，面临着底物反应位点远离手性配体的问题，它的不对称催化能力受到很大的限制。因此，如何提高金催化的有机反应的对映选择性仍然是金催化领域目前所面临的一个挑战。为了提高金催化的手性选择性，轴手性的双磷配体或者手性磷酸阴离子被广泛应用于一价金催化的有机反应中。相对而言，三价金络合物是四配位的平面正方形结构，可以与手性配体配位获得更为“拥挤”的手性空间环境，使得底物与配体之间的距离比较邻近，从而有利于不对称诱导。因此，选用适当的手性配体，发展一些易于合成的、具有多可调位点的、稳定性好的新型三价金手性络合物作为催化剂用于不对称催化反应将对拓展金催化的不对称反应领域具有重要的意义。
发明内容
本发明的目的在于提供一种稳定的手性三价金络合物及其制备方法和应用，旨在解决三价金盐由于稳定性差，制备相应的络合物比较困难，以及在反应过程中催化活性太高，造成反应物的官能团兼容性差及产物选择性差，不适作为催化剂、用于催化有机反应的问题。
本发明是这样实现的，一种手性三价金络合物，所述手性三价金络合物由两个碳-金共价键、一个氧-金共价键以及一个氮-金配位键构成，具有手性联萘酚和噁唑啉配体骨架，或具有手性联萘酚和邻位取代吡啶配体骨架，所述手性三价金络合物具有下述通式I或通式II的化合物，以及所述通式I或通式II的消旋体和旋光异构体，
其中，R1、R2分别独立选自H、卤素、C1～C10的烃基、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基，所述n的取值范围满足0≤n≤2，且R1、R2相同或不同；
R3、R4分别独立选自H、卤素、C1～C10的烃基、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；所述m的取值范围满足0≤m≤4，且R3、R4相同或不同；
R5选自H、卤素、C1～C10的烃基、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；所述o的取值范围满足0≤o≤4；
R6、R7分别独立选自H、C1～C10的烃基、苯基、取代苯基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；或R6、R7为通过C2～C4的碳链，含氮、氧、硫的碳链连接成环；R6、R7相同或不同；
R8、R9分别独立选自H、卤素、C1～C10的烃基、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；所述p的取值范围满足0≤p≤4，所述q的取值范围满足0≤q≤4，R8、R9相同或不同；
X为CH2、NH、O、C＝O或者不含任何原子。
相应的，一种手性三价金络合物的制备方法，包括以下步骤：
提供消旋的或具有旋光活性的如式1所述结构的联萘酚衍生物、如式2所述结构的噁唑啉-金(III)二氯化物或如式3所述结构的2-取代吡啶-金(III)二氯化物；
将所述联萘酚衍生物、噁唑啉-金(III)二氯化物或2-取代吡啶-金(III)二氯化物溶于有机溶剂中，在碱存在条件下发生如下化学反应，得到手性三价金络合物，其反应通式如下：
以及，一种上述手性三价金络合物的用途，所述手性三价金络合物用于催化2-炔基苯甲醛与原甲酸三酯的反应。
本发明提供的手性三价金络合物，基于手性联萘酚配体与噁唑啉或邻位取代吡啶配体设计获得，通过两个碳-金共价键、一个氧-金共价键以及一个氮-金配位键得到金原子中心呈电中性的三价金络合物，具有很好的结构稳定性。其成键模式独特，显著提高了三价金络合物稳定性，改善了其催化活性，并在催化2-炔基苯甲醛与原甲酸三酯的反应中获得了优秀的化学选择性和区域选择性。本发明提供的稳定手性三价金络合物，可以应用于催化2-炔基苯甲醛与原甲酸三酯的反应，特别是催化2-炔基苯甲醛与原甲酸三酯的(半)缩醛化-环异构化串联反应。且所述手性三价金络合物作为催化剂时，在稳定性和催化活性上实现了“平衡”，在2-炔基苯甲醛与原甲酸三酯的反应中可以控制不同类型反应产物的生成，解决了大多数三价金络合物不稳定和催化反应的活性太高而造成很多副产物产生的问题。此外，由于所述稳定手性三价金络合物具有手性，有望广泛应用于多种类型的不对称有机反应以及多肽和蛋白质的修饰当中，为三价金催化剂的发展提供一类可以被广泛应用的新产品。
本发明提供了一种简便高效地制备温度手性三价金络合物的方法，可以快速地合成一系列金(III)络合物，组成金(III)催化剂“库”或“工具箱”，解决目前稳定三价金络合物比较难制备的技术难题，对于促进三价金络合物在多种催化不对称有机反应中的应用具有重要的意义。此外，本发明制备方法简单，反应条件温和，反应原料或前体易得，产率高，分离纯化极其方便(不需要传统的柱层析方法)，适于规模化生产(几十克量级，解决一般三价金络合物制备量比较小的技术难题)，作为催化剂用于多种有机反应中具有非常实用的价值。
本发明提供的手性三价金络合物的用途，直接作为催化剂用于催化2-炔基苯甲醛与原甲酸三酯的半缩醛化-环异构化串联反应，可以专一地得到单一的六元环环化产物，无五元环环化产物生成，表现出优异的区域选择性。在添加共催化剂，特别是添加樟脑磺酸的情况下，形成活性更高的金(III)催化剂体系用于催化2-炔基苯甲醛与原甲酸三酯的缩醛化-环异构化串联反应时，专一地得到单一的carboalkoxylation五元环产物3-烷氧基茚酮，与不添加共催化剂的条件相比，对同一反应底物表现出优异的化学选择性。
具体实施方式
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明实施例提供了一种手性三价金络合物，所述手性三价金络合物由两个碳-金共价键、一个氧-金共价键以及一个氮-金配位键构成，具有手性联萘酚和噁唑啉配体骨架，或具有手性联萘酚和邻位取代吡啶配体骨架，所述手性三价金络合物具有下述通式I或通式II的化合物，以及所述通式I或通式II的消旋体和旋光异构体，
其中，R1、R2分别独立选自H、卤素、C1～C10的烃基、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基，所述n的取值范围满足0≤n≤2，且R1、R2相同或不同；
R3、R4分别独立选自H、卤素、C1～C10的烃基、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；所述m的取值范围满足0≤m≤4，且R3、R4相同或不同；
R5选自H、卤素、C1～C10的烃基、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；所述o的取值范围满足0≤o≤4；
R6、R7分别独立选自H、C1～C10的烃基、苯基、取代苯基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；或R6、R7为通过C2～C4的碳链，含氮、氧、硫的碳链连接成环；R6、R7相同或不同；
R8、R9分别独立选自H、卤素、C1～C10的烃基、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；所述p的取值范围满足0≤p≤4，所述q的取值范围满足0≤q≤4，R8、R9相同或不同；
X为CH2、NH、O、C＝O或者不含任何原子。
其中，当R6、R7不同时，所述通式I包括其消旋体和旋光异构体。
本发明实施例所述手性三价金络合物由两个碳-金共价键、一个氧-金共价键以及一个氮-金配位键构成，以手性联萘酚和噁唑啉配体、或手性联萘酚和邻位取代吡啶配体作为骨架结构，赋予所述手性三价金络合物优异的结构稳定性，同时改善其催化活性，使得其可以作为催化剂用于催化有机反应。
优选的，所述n＝2时，两个相邻的R1、R2同为C3～C7脂肪环或芳香环。
优选的，所述m≥2时，两个相邻的R3、R4同为C3～C7脂肪环或芳香环。
优选的，所述o≥2时，两个相邻的R5同为C3～C7脂肪环或芳香环。
优选的，所述p≥2时，两个相邻的R8同为C3～C7脂肪环或芳香环。
优选的，所述q≥2时，两个相邻的R9同为C3～C7脂肪环或芳香环。
优选的，所述X不含原子时，相邻的R8、R9同为芳香环。
上述优选的结构，更有利于获得结构稳定的手性三价金络合物。当然，应当理解，上述优选情形可以择一或任意组合出现在同一实施例中。
作为具体优选实施例，所述手性三价金络合物包括下述结构的化合物，下述结构化合物的对映体、消旋体和非对映异构体，
上述优选的具体结构，结构稳定性强，且在2-炔基苯甲醛与原甲酸三酯的反应，特别是2-炔基苯甲醛与原甲酸三酯的(半)缩醛化-环异构化串联反应，具有非常优异的催化效果，因此，更优选为作为2-炔基苯甲醛与原甲酸三酯的反应、特别是2-炔基苯甲醛与原甲酸三酯的(半)缩醛化-环异构化串联反应的催化剂。
本发明实施例提供的手性三价金络合物，基于手性联萘酚配体与噁唑啉或邻位取代吡啶配体设计获得，通过两个碳-金共价键、一个氧-金共价键以及一个氮-金配位键得到金原子中心呈电中性的三价金络合物。其成键模式独特，显著提高了三价金络合物稳定性，改善了其催化活性，并在催化2-炔基苯甲醛与原甲酸三酯的反应中获得了优秀的化学选择性和区域选择性。本发明实施例提供的稳定手性三价金络合物，可以应用于催化2-炔基苯甲醛与原甲酸三酯的反应，特别是催化2-炔基苯甲醛与原甲酸三酯的(半)缩醛化-环异构化串联反应。且所述手性三价金络合物作为催化剂时，在稳定性和催化活性上实现了“平衡”，在2-炔基苯甲醛与原甲酸三酯的反应中可以控制不同类型反应产物的生成，解决了大多数三价金络合物不稳定和催化反应的活性太高而造成很多副产物产生的问题。此外，由于所述稳定手性三价金络合物具有手性，有望广泛应用于多种类型的不对称有机反应以及多肽和蛋白质的修饰当中，为三价金催化剂的发展提供一类可以被广泛应用的新产品。
本发明实施例所述手性三价金络合物可以通过下述方法制备获得。
相应的，一种手性三价金络合物的制备方法，包括以下步骤：
S01.提供消旋的或具有旋光活性的如式1所述结构的联萘酚衍生物、如式2所述结构的噁唑啉-金(III)二氯化物或如式3所述结构的2-取代吡啶-金(III)二氯化物；
S02.将所述联萘酚衍生物、噁唑啉-金(III)二氯化物或2-取代吡啶-金(III)二氯化物溶于有机溶剂中，在碱存在条件下发生如下化学反应，得到手性三价金络合物，其反应通式如下：
具体的，上述步骤S01中，所述联萘酚衍生物、噁唑啉-金(III)二氯化物、2-取代吡啶-金(III)二氯化物可以通过购买获得，可以自行制备获得。所述联萘酚衍生物、噁唑啉-金(III)二氯化物、2-取代吡啶-金(III)二氯化物结构中各取代基的选用与上述手性三价金络合物结构中对应取代基的选用一致。
上述步骤S02中，将所述联萘酚衍生物、噁唑啉-金(III)二氯化物或2-取代吡啶-金(III)二氯化物溶于有机溶剂中，所述有机溶剂为甲醇、乙醇、丙醇、异丙醇、丁醇、四氢呋喃、甲苯、二氧六环，二氯甲烷、氯仿、DCE中的至少一种。优选的有机溶剂，不仅对反应物具有较好的溶解性能，而且具有较好的反应稳定性，不与反应物发生化学反应。
本发明实施例所述联萘酚衍生物与所述噁唑啉-金(III)二氯化物或所述2-取代吡啶-金(III)二氯化物的反应，在碱性条件下，有利于反应的进行。具体的，所述碱包括有机碱和无机碱，其中，所述有机碱包括三乙胺、三丁胺、N-甲基吗啡啉、N,N-二乙基异丙胺、1,4-二氮杂二环[2.2.2]辛烷，所述无机碱包括碳酸钠，碳酸钾，碳酸铯，甲醇钠，叔丁醇钾。
本发明实施例反应条件温和，在室温下即可实现，所述室温为10-30℃的温度。
进一步的，所述联萘酚衍生物、所述噁唑啉-金(III)二氯化物或2-取代吡啶-金(III)二氯化物、所述碱的摩尔比为0.90～1.25：1.0：1.80～2.50或1.0：0.90～1.25：2.0。优选的物质比例，有利于所述联萘酚衍生物与所述噁唑啉-金(III)二氯化物或所述2-取代吡啶-金(III)二氯化物的反应朝正方向进行，且利于获得杂质少、纯度高的产物。作为具体优选实施例，所述联萘酚衍生物、所述噁唑啉-金(III)二氯化物或2-取代吡啶-金(III)二氯化物、所述碱的摩尔比为1.05：1：2.1。
其中，当所述1,1’-联萘酚衍生物为R-构型时，式I或式II结构中与Au原子相连的手性碳是S-构型；
当所述1,1’-联萘酚衍生物(式1)为S-构型时，式I或式II中与Au原子相连的手性碳是R-构型。
经过上述步骤S02后，将反应体系进行过滤、洗涤处理，即可得到本发明实施例反应产物。
本发明实施例提供了一种简便高效地制备温度手性三价金络合物的方法，可以快速地合成一系列金(III)络合物，组成金(III)催化剂“库”或“工具箱”，解决目前稳定三价金络合物比较难制备的技术难题，对于促进三价金络合物在多种催化不对称有机反应中的应用具有重要的意义。此外，本发明实施例制备方法简单，反应条件温和，反应原料或前体易得，产率高，分离纯化极其方便(不需要传统的柱层析方法)，适于规模化生产(几十克量级，解决一般三价金络合物制备量比较小的技术难题)，作为催化剂用于多种有机反应中具有非常实用的价值。
以及，一种上述手性三价金络合物的用途，所述手性三价金络合物用于催化2-炔基苯甲醛与原甲酸三酯的反应。
优选的，所述手性三价金络合物特别适用于2-炔基苯甲醛与原甲酸三酯的(半)缩醛化-环异构化串联反应。
本发明实施例上述手性三价金络合物的用途，可以选择性地催化2-炔基苯甲醛与原甲酸三酯的反应，特别是催化2-炔基苯甲醛与原甲酸三酯的(半)缩醛化-环异构化串联反应，并在添加共催化剂与不添加共催化剂的情况下表现出优异的化学选择性和区域选择性。
进一步的，所述手性三价金络合物在无添加和有添加共催化剂磺酸的条件下展示出不同的催化活性，从而很好地控制了反应的化学选择性及区域选择性。具体的，所述手性三价金络合物化学选择性及区域选择性具体体现如下：
作为一个具体实施例，在不添加共催化剂磺酸的情况下，所述手性三价金络合物催化2-炔基苯甲醛与原甲酸三酯发生半缩醛化-环异构化串联反应，得到单一的六元环化产物，结构如式5所示，表现出优异的区域选择性。具体的，在适当的溶剂中，将0.5-5mol％、更优选为2.5mol％的所述金(III)络合物与2-炔基苯甲醛与2-6当量、更优选为6当量的原甲酸三酯混合，在室温到60℃的反应条件下，搅拌反应8-24小时，获得单一的六元环化产物，结构如式5所示。其中，所述有机溶剂为乙腈、四氢呋喃、甲苯、二氧六环、二氯甲烷、氯仿、DCE中的一种或其中几种的混合溶剂；所述的原甲酸三酯包括原甲酸三甲酯、原甲酸三乙酯、原甲酸三丙酯、原甲酸三异丙酯和原甲酸三丁酯。
作为一个具体实施例，在添加共催化剂磺酸的情况下，所述手性三价金络合物催化2-炔基苯甲醛与原甲酸三酯发生缩醛化-环异构化串联反应，得到carboalkoxylation五元环化产物，结构如式6所示，与不添加共催化剂的条件相比，对同一反应底物表现出优异的化学选择性。具体的，在适当的溶剂中，将0.5-5mol％、更优选为2.5mol％的所述金(III)络合物与2-炔基苯甲醛与2-6当量、更优选为6当量的原甲酸三酯混合，加入5-25mol％、更优选为20mol％的磺酸，在室温到60℃的反应条件下，搅拌反应8-24小时，可以获得五元环化产物6。其中，所述有机溶剂为乙腈、四氢呋喃、甲苯、二氧六环、二氯甲烷、氯仿、DCE中的一种或其中几种的混合溶剂；所述的原甲酸三酯包括原甲酸三甲酯、原甲酸三乙酯、原甲酸三丙酯、原甲酸三异丙酯和原甲酸三丁酯；所述磺酸包括苯磺酸、对甲基苯磺酸、樟脑苯磺酸、甲基磺酸和三氟甲基磺酸。
上述两个具体实施例的反应式如下所示：
其中，[Au]为：
式5、式6中，Ra选自H、卤素、C1～C10的烃基、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，杂芳基为呋喃基、噻吩基或吡啶基；所述y的取值范围满足0≤y≤4，当y≥2时，两个相邻的Ra可并为C3～C7脂肪环或芳香环，Ra可以相同也可以不同；Rb选自H、C1～C10的烃基、芳基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，杂芳基为呋喃基、噻吩基或吡啶基；Rc选自C1～C10的烃基或苄基。
在具体实施例中，所述手性三价金络合物用于2-炔基苯甲醛与原甲酸三酯的(半)缩醛化-环异构化串联反应。作为一个优选实施例，所述原甲酸三酯包括原甲酸三甲酯、原甲酸三乙酯、原甲酸三丙酯、原甲酸三异丙酯和原甲酸三丁酯。作为另一个优选实施例，所述磺酸包括苯磺酸、对甲基苯磺酸、樟脑苯磺酸、甲基磺酸和三氟甲基磺酸。作为再一个优选实施例，用于所述(半)缩醛化-环异构化串联的有机溶剂为乙腈、四氢呋喃、甲苯、二氧六环、二氯甲烷、氯仿、DCE中的至少一种。
进一步优选的，作为催化剂的所述手性三价金络合物优选为上述手性三价金络合物优选的化合物，化合物的对映体、消旋体和非对映异构体，从而获得更佳的催化效果，进而具有更加的化学选择性和区域选择性。
本发明实施例提供的手性三价金络合物的用途，直接作为催化剂用于催化2-炔基苯甲醛与原甲酸三酯的半缩醛化-环异构化串联反应，可以专一地得到单一的六元环环化产物，无五元环环化产物生成，表现出优异的区域选择性。在添加共催化剂，特别是添加樟脑磺酸的情况下，形成活性更高的金(III)催化剂体系用于催化2-炔基苯甲醛与原甲酸三酯的缩醛化-环异构化串联反应时，专一地得到单一的carboalkoxylation五元环产物3-烷氧基茚酮，与不添加共催化剂的条件相比，对同一反应底物表现出优异的化学选择性。
下面结合具体实施例进行说明。
实施例1：金(III)络合物(R)-1的合成
将S-构型的联萘酚(S)-1,1’-联萘酚(0.22mmol)，基于噁唑啉配体骨架的2-[2’-(4’,4’-二甲基)恶唑啉基]苯基二氯化金(0.20mmol),无水碳酸铯(0.44mmol)以及甲醇(10mL)置于25mL的圆底烧瓶中。室温下搅拌，观察到慢慢有橙红色沉淀产生，反应2小时后，TLC检测(乙酸乙酯：石油醚1:3)反应完全，过滤，所得橙红色固体用适量甲醇洗涤(或者经硅胶柱层析)，得到橙红色固体为R-构型的金(III)络合物(R)-1(112mg，收率85％)。1H NMR(400MHz,CDCl3)δ7.92(d,J＝9.9Hz,1H),7.67(dd,J＝9.1,3.6Hz,2H),7.52(d,J＝7.1Hz,1H),7.47(d,J＝7.8Hz,1H),7.36–7.30(m,2H),7.25–7.15(m,4H),7.13(dd,J＝10.8,4.3Hz,1H),7.07–6.94(m,2H),6.77(dd,J＝6.3,3.1Hz,1H),6.64(d,J＝9.8Hz,1H),4.62(d,J＝8.5Hz,1H),4.56(d,J＝8.5Hz,1H),1.84(s,6H).13C NMR(101MHz,CDCl3)δ200.9,177.3,170.9,147.2,144.9,140.5,133.6,132.7,130.6,130.4,130.3,129.7,129.6,129.0,128.9,128.6,128.2,127.6,126.6,126.0,126.0,125.0,121.8,120.72,120.68,84.6,70.6,67.4,27.2,26.9.HRMS(ESI):Calcd.for[C31H25AuNO3]+656.1494,found656.1451.
实施例2：金(III)络合物(S)-1的合成
将R-构型的联萘酚(S)-1,1’-联萘酚(0.22mmol)，基于噁唑啉配体骨架的2-[2’-(4’,4’-二甲基)恶唑啉基]苯基二氯化金(0.20mmol),无水碳酸铯(0.44mmol)以及甲醇(10mL)置于25mL的圆底烧瓶中。室温下搅拌，观察到慢慢有橙红色沉淀产生，反应2小时后，TLC检测(乙酸乙酯：石油醚1:3)反应完全，过滤，所得橙红色固体用适量甲醇洗涤(或者经硅胶柱层析)，得到橙红色固体为R-构型的金(III)络合物(S)-1(115mg，收率88％)。1H NMR(400MHz,CDCl3)δ7.92(d,J＝9.9Hz,1H),7.67(dd,J＝9.1,3.6Hz,2H),7.52(d,J＝7.0Hz,1H),7.47(d,J＝7.8Hz,1H),7.37–7.29(m,2H),7.21(ddd,J＝14.1,8.2,4.4Hz,4H),7.13(dd,J＝10.8,4.3Hz,1H),7.06–6.96(m,2H),6.77(dd,J＝6.1,3.3Hz,1H),6.64(d,J＝9.8Hz,1H),4.62(d,J＝8.5Hz,1H),4.56(d,J＝8.5Hz,1H),1.84(s,6H).13C NMR(101MHz,CDCl3)δ200.8,177.3,170.9,147.2,144.9,140.5,133.6,132.7,130.6,130.4,130.3,129.7,129.6,129.0,128.9,128.6,128.2,127.6,126.6,126.0,125.9,125.1,121.9,120.7,120.7,84.6,70.6,67.4,27.2,26.9.HRMS(ESI):Calcd.for[C31H25AuNO3]+656.1494,found 656.1448.
实施例3：金(III)络合物(R,S)-2的合成
具体操作参见实施例1，橙红色固体，收率87％。1H NMR(400MHz,CDCl3)δ7.93(d,J＝9.9Hz,1H),7.68(d,J＝8.8Hz,2H),7.51(d,J＝7.5Hz,1H),7.44(d,J＝7.8Hz,1H),7.34(dd,J＝12.3,7.5Hz,2H),7.27–7.16(m,4H),7.11(t,J＝7.5Hz,1H),7.02(p,J＝7.1Hz,2H),6.83–6.74(m,1H),6.65(d,J＝9.8Hz,1H),4.77(t,J＝8.6Hz,2H),4.67(td,J＝7.6,3.5Hz,1H),3.13–2.97(m,1H),1.06(d,J＝7.1Hz,3H),0.96(d,J＝6.8Hz,3H).13C NMR(101MHz,CDCl3)δ200.8,178.6,170.2,147.0,145.0,140.6,133.8,132.7,130.6,130.5,130.4,129.9,129.129,129.1,128.9,128.7,128.2,127.7,126.7,126.5,126.0,125.4,121.6,120.9,120.8,72.7,70.2,67.7,28.8,18.8,14.6.HRMS(ESI):Calcd.for[C32H27AuNO3]+670.1651,found 670.1592.
实施例4：金(III)络合物(R,R)-2的合成
具体操作参见实施例1，橙红色固体，收率94％。1H NMR(400MHz,CDCl3)δ7.91(d,J＝9.9Hz,1H),7.69(dd,J＝8.8,4.6Hz,2H),7.54(d,J＝7.3Hz,1H),7.46(d,J＝7.7Hz,1H),7.33(dd,J＝7.1,1.5Hz,1H),7.30–7.17(m,5H),7.14(dd,J＝11.0,4.1Hz,1H),7.09–6.96(m,2H),6.78(d,J＝7.4Hz,1H),6.62(d,J＝9.8Hz,1H),4.75(dt,J＝15.1,9.2Hz,2H),4.69–4.58(m,1H),3.00–2.81(m,1H),1.08(d,J＝7.1Hz,3H),0.95(d,J＝6.9Hz,3H).13CNMR(101MHz,CDCl3)δ200.7,178.6,170.6,147.1,144.9,140.6,133.6,132.9,130.5,130.4,129.7,129.3,129.1,129.0,128.7,128.2,127.6,126.7,126.5,126.0,125.4,121.7,120.80,120.76,73.1,70.1,67.6,29.2,18.8,15.1.HRMS(ESI):Calcd.for[C32H27AuNO3]+670.1651,found 670.1583.
实施例5：金(III)络合物(S,S)-2的合成
具体操作参见实施例1，橙红色固体，收率91％。1H NMR(400MHz,CDCl3)δ7.91(d,J＝9.9Hz,1H),7.67(dd,J＝7.8,4.1Hz,2H),7.54(d,J＝7.5Hz,1H),7.45(d,J＝7.8Hz,1H),7.33(d,J＝7.7Hz,1H),7.27–7.10(m,6H),7.07–6.95(m,2H),6.75(d,J＝7.9Hz,1H),6.60(d,J＝9.8Hz,1H),4.78(dt,J＝15.1,9.1Hz,2H),4.70–4.61(m,1H),2.92(qd,J＝10.8,6.8Hz,1H),1.09(d,J＝7.1Hz,3H),0.95(d,J＝6.9Hz,3H).13C NMR(101MHz,CDCl3)δ200.6,178.6,170.5,147.1,144.8,140.6,133.5,132.9,130.5,130.4,129.7,129.3,129.1,129.0,128.71,128.68,128.2,127.6,126.7,126.5,126.0,125.3,121.6,120.8,120.7,73.1,70.1,67.6,29.2,18.8,15.1.HRMS(ESI):Calcd.for[C32H27AuNO3]+670.1651,found670.1588.
实施例6：金(III)络合物(S,R)-2的合成
具体操作参见实施例1，橙红色固体，收率87％。1H NMR(400MHz,CDCl3)δ7.93(d,J＝9.9Hz,1H),7.73–7.64(m,2H),7.51(d,J＝7.3Hz,1H),7.44(d,J＝7.7Hz,1H),7.39–7.30(m,2H),7.27–7.15(m,4H),7.11(dd,J＝11.0,4.1Hz,1H),7.07–6.99(m,2H),6.84–6.75(m,1H),6.66(d,J＝9.8Hz,1H),1.06(d,J＝7.1Hz,3H),0.96(d,J＝6.8Hz,3H).13C NMR(101MHz,CDCl3)δ200.9,178.6,170.2,147.0,145.1,140.6,133.8,132.8,130.5,130.4,129.8,129.13,129.10,128.9,128.81,128.75,128.2,127.7,126.8,126.6,126.1,125.4,121.6,120.9,120.8,72.7,70.2,67.7,28.8,18.8,14.6.HRMS(ESI):Calcd.for[C32H27AuNO3]+670.1651,found 670.1664.
实施例7：金(III)络合物(R,S)-3的合成
具体操作参见实施例1，橙红色固体，收率94％。1H NMR(4000MHz,CDCl3)δ7.88(d,J＝9.9Hz,1H),7.66–7.61(m,1H),7.59(d,J＝8.9Hz,1H),7.54–7.39(m,7H),7.23(ddd,J＝18.8,13.3,7.9Hz,5H),7.06(t,J＝7.2Hz,1H),7.02–6.91(m,3H),6.67(d,J＝7.7Hz,1H),6.58(d,J＝9.8Hz,1H),5.72(dd,J＝9.9,6.1Hz,1H),5.23(t,J＝9.5Hz,1H),4.94(dd,J＝9.0,6.1Hz,1H).13C NMR(101MHz,CDCl3)δ200.5,179.2,170.6,146.9,144.8,141.0,138.6,133.8,132.8,130.5,130.3,130.2,129.7,129.2,129.0,128.9,128.6,128.1,127.9,127.4,126.7,126.5,125.9,125.0,121.6,120.65,120.59,79.8,70.2,65.7.HRMS(ESI):Calcd.for[C35H25AuNO3]+704.1494,found 704.1411.
实施例8：金(III)络合物(R,R)-3的合成
具体操作参见实施例1，橙红色固体，收率93％。1H NMR(400MHz,CDCl3)δ7.89(d,J＝9.9Hz,1H),7.67–7.62(m,1H),7.60(d,J＝8.9Hz,1H),7.56–7.38(m,7H),7.33–7.13(m,5H),7.10–6.91(m,4H),6.73–6.64(m,1H),6.59(d,J＝9.8Hz,1H),5.72(dd,J＝10.0,6.0Hz,1H),5.20(t,J＝9.5Hz,1H),4.89(dd,J＝9.0,6.1Hz,1H).13C NMR(101MHz,CDCl3)δ200.6,179.2,170.5,146.9,144.9,140.8,138.7,133.8,132.8,130.5,130.3,130.2,129.6,129.2,129.0,128.90,128.88,128.6,128.5,128.1,127.9,127.4,126.8,126.5,126.0,125.0,121.6,120.7,120.6,79.9,70.2,65.7.HRMS(ESI):Calcd.for[C35H25AuNO3]+704.1494,found 704.1480.
实施例9：金(III)络合物(S,S)-3的合成
具体操作参见实施例1，橙红色固体，收率96％。1H NMR(400MHz,CDCl3)δ7.89(d,J＝9.9Hz,1H),7.68–7.62(m,1H),7.60(d,J＝8.9Hz,1H),7.55–7.38(m,7H),7.23(ddd,J＝21.8,12.6,6.7Hz,5H),7.09–6.91(m,4H),6.68(d,J＝7.5Hz,1H),6.59(d,J＝9.8Hz,1H),5.71(dd,J＝9.9,6.0Hz,1H),5.20(t,J＝9.5Hz,1H),4.90(dd,J＝9.0,6.1Hz,1H).13C NMR(101MHz,CDCl3)δ200.5,179.2,170.6,146.9,144.9,140.9,138.7,133.8,132.8,130.5,130.3,130.2,129.6,129.2,129.0,128.9,128.6,128.6,128.1,127.9,127.4,126.8,126.5,125.9,125.0,121.6,120.7,120.6,79.9,70.2,65.7.HRMS(ESI):Calcd.for[C35H25AuNO3]+704.1494,found704.1449.
实施例10：金(III)络合物(S,R)-3的合成
具体操作参见实施例1，橙红色固体，收率94％。1H NMR(400MHz,CDCl3)δ7.91(d,J＝9.8Hz,1H),7.63(dd,J＝6.0,3.1Hz,1H),7.58(d,J＝8.9Hz,1H),7.53–7.35(m,9H),7.25(dt,J＝14.6,6.6Hz,2H),7.17(t,J＝7.3Hz,1H),7.09(t,J＝7.4Hz,1H),6.99(dd,J＝6.2,3.1Hz,2H),6.91(d,J＝8.9Hz,1H),6.74(dd,J＝5.9,3.3Hz,1H),6.65(d,J＝9.8Hz,1H),5.67(dd,J＝9.7,6.0Hz,1H),5.16(t,J＝9.4Hz,1H),4.86(dd,J＝8.8,6.2Hz,1H).13C NMR(101MHz,CDCl3)δ200.7,179.4,170.3,147.1,144.9,141.4,138.3,134.2,132.6,130.5,130.4,130.34,130.32,129.2,129.02,128.97,128.9,128.8,128.6,128.2,127.9,127.0,126.7,126.5,126.0,125.1,121.5,120.7,120.6,80.00,70.1,65.6.HRMS(ESI):Calcd.for[C35H25AuNO3]+704.1494,found704.1495.
实施例11：金(III)络合物(R,S)-4的合成
具体操作参见实施例1，橙红色固体，收率92％。1H NMR(400MHz,CDCl3)δ7.95(d,J＝9.9Hz,1H),7.76–7.65(m,2H),7.53(d,J＝7.1Hz,1H),7.49(d,J＝7.7Hz,1H),7.45–7.35(m,5H),7.33–7.10(m,8H),7.08–6.99(m,2H),6.81(dd,J＝5.8,3.7Hz,1H),6.68(d,J＝9.8Hz,1H),5.00–4.86(m,1H),4.83–4.70(m,2H),3.99(dd,J＝13.7,3.2Hz,1H),3.12(dd,J＝13.7,9.4Hz,1H).13C NMR(101MHz,CDCl3)δ200.7,179.0,170.2,147.0,145.0,140.7,135.9,133.9,132.8,130.6,130.4,129.8,129.6,129.2,129.1,129.0,128.9,128.82,128.76,128.2,127.8,127.1,126.7,126.6,126.1,125.4,121.7,120.9,120.8,76.6,70.3,63.9,39.6.HRMS(ESI):Calcd.for[C36H27AuNO3]+718.1651,found 718.1602.
实施例12：金(III)络合物(R,R)-4的合成
具体操作参见实施例1，橙红色固体，收率91％。1H NMR(400MHz,CDCl3)δ7.94(d,J＝9.9Hz,1H),7.69(dd,J＝9.1,3.1Hz,2H),7.53(dd,J＝15.7,7.5Hz,2H),7.39(dt,J＝14.8,7.3Hz,4H),7.33–7.21(m,6H),7.17(dd,J＝14.0,7.2Hz,2H),7.07–6.96(m,2H),6.82–6.72(m,1H),6.65(d,J＝9.8Hz,1H),4.93(qd,J＝9.5,3.2Hz,1H),4.82(t,J＝9.1Hz,1H),4.67(dd,J＝8.6,7.3Hz,1H),3.98(dd,J＝13.6,3.2Hz,1H),3.12(dd,J＝13.6,9.3Hz,1H).13C NMR(101MHz,CDCl3)δ200.5,179.0,170.6,147.2,144.9,140.8,136.1,133.8,132.9,130.4,130.3,129.7,129.5,129.2,129.1,129.0,128.9,128.8,128.2,127.7,127.2,126.7,126.6,126.0,125.3,121.7,120.8,120.8,70.3,64.0,39.6.HRMS(ESI):Calcd.for[C36H27AuNO3]+718.1651,found718.1568.
实施例13：(O^C,C^N)-Au(III)络合物(S,S)-4的合成
具体操作参见实施例1，橙红色固体，收率93％。1H NMR(400MHz,CDCl3)δ7.94(d,J＝9.9Hz,1H),7.69(dd,J＝9.2,2.9Hz,2H),7.55(d,J＝6.9Hz,1H),7.51(d,J＝7.7Hz,1H),7.45–7.34(m,4H),7.33–7.13(m,9H),7.09–6.97(m,2H),6.77(d,J＝7.3Hz,1H),6.65(d,J＝9.8Hz,1H),4.99–4.89(m,1H),4.83(t,J＝9.1Hz,1H),4.68(dd,J＝8.7,7.3Hz,1H),3.98(dd,J＝13.6,3.2Hz,1H),3.12(dd,J＝13.6,9.3Hz,1H).13C NMR(101MHz,CDCl3)δ200.6,179.0,170.6,147.2,144.9,140.8,136.1,133.8,132.9,130.4,130.3,129.7,129.5,129.2,129.1,129.00,128.96,128.8,128.2,127.7,127.2,126.7,126.6,126.0,125.3,121.7,120.9,120.8,76.9,70.3,64.0,39.6.HRMS(ESI):Calcd.for[C36H27AuNO3]+718.1651,found 718.1595.
实施例14：金(III)络合物(S,R)-4的合成
具体操作参见实施例1，橙红色固体，收率88％。1H NMR(400MHz,CDCl3)δ7.94(d,J＝9.9Hz,1H),7.75–7.65(m,2H),7.53(d,J＝7.2Hz,1H),7.48(d,J＝7.7Hz,1H),7.45–7.34(m,5H),7.33–7.09(m,7H),7.08–6.98(m,2H),6.80(dd,J＝6.4,2.9Hz,1H),6.68(d,J＝9.8Hz,1H),5.02–4.85(m,1H),4.85–4.68(m,2H),3.99(dd,J＝13.7,3.2Hz,1H),3.12(dd,J＝13.8,9.4Hz,1H).13C NMR(101MHz,CDCl3)δ200.7,179.0,170.2,147.0,145.0,140.7,135.9,133.9,132.8,130.6,130.4,129.8,129.6,129.2,129.1,129.0,128.9,128.8,128.7,128.2,127.8,127.1,126.7,126.6,126.1,125.4,121.6,121.0,120.8,70.3,63.9,39.6.HRMS(ESI):Calcd.for[C36H27AuNO3]+718.1651,found 718.1583.
实施例15：金(III)络合物(R)-5的合成
具体操作参见实施例1，橙红色固体，收率87％。1H NMR(400MHz,CDCl3)δ9.00(d,J＝4.9Hz,1H),7.93–7.87(m,1H),7.73–7.66(m,2H),7.60(d,J＝7.7Hz,1H),7.54–7.41(m,3H),7.37–7.29(m,2H),7.26(d,J＝10.0Hz,1H),7.22–7.17(m,1H),7.09–7.04(m,1H),7.02(t,J＝7.3Hz,2H),6.99–6.94(m,1H),6.74(t,J＝6.7Hz,1H),6.45(d,J＝8.3Hz,1H),6.12(d,J＝9.9Hz,1H),5.61(d,J＝7.7Hz,1H),4.48(d,J＝14.6Hz,1H),3.92(d,J＝14.7Hz,1H).13C NMR(101MHz,CDCl3)δ199.5,169.6,156.6,149.6,144.6,143.3,141.0,137.9,136.1,133.1,130.5,130.4,130.0,129.7,128.9,128.7,128.1,127.0,126.8,126.6,126.3,126.0,125.8,123.8,123.6,121.7,121.4,120.8,68.8,48.0.HRMS(ESI):Calcd.for[C32H23AuNO2]+650.1389,found650.1371.
实施例16：金(III)络合物(S)-5的合成
具体操作参见实施例1，橙红色固体，收率84％。1H NMR(400MHz,CDCl3)δ9.00(d,J＝4.8Hz,1H),7.89(t,J＝7.7Hz,1H),7.75–7.66(m,2H),7.59(d,J＝7.7Hz,1H),7.55–7.40(m,3H),7.37–7.29(m,2H),7.26(d,J＝10.0Hz,1H),7.23–7.18(m,1H),7.06(dd,J＝9.2,3.0Hz,1H),7.02(t,J＝7.1Hz,2H),6.99–6.94(m,1H),6.75(t,J＝6.7Hz,1H),6.45(d,J＝8.2Hz,1H),6.13(d,J＝9.8Hz,1H),5.61(d,J＝7.7Hz,1H),4.47(d,J＝14.6Hz,1H),3.92(d,J＝14.6Hz,1H).13C NMR(101MHz,CDCl3)δ199.6,169.7,156.4,149.4,144.7,143.4,141.1,137.9,136.1,133.1,130.5,130.4,130.1,129.6,128.9,128.6,128.2,127.0,126.8,126.6,126.3,126.0,125.8,123.8,123.6,121.8,121.5,120.8,68.8,47.9.HRMS(ESI):Calcd.for[C32H23AuNO2]+650.1389,found 650.1362.
实施例17：金(III)络合物(R)-6的合成
具体操作参见实施例1，橙红色固体，收率86％。1H NMR(400MHz,CDCl3)δ9.33(d,J＝4.8Hz,1H),8.35(d,J＝7.1Hz,1H),8.23(td,J＝7.7,1.3Hz,1H),7.88(t,J＝5.9Hz,1H),7.76–7.58(m,3H),7.51(d,J＝7.6Hz,1H),7.41–7.31(m,2H),7.30–7.21(m,4H),7.17(d,J＝8.9Hz,1H),7.08(td,J＝7.7,1.4Hz,1H),7.03(t,J＝7.3Hz,1H),6.96(t,J＝7.0Hz,1H),6.44(d,J＝8.2Hz,1H),6.16(d,J＝9.9Hz,1H).13C NMR(101MHz,CDCl3)δ198.8,189.8,169.0,149.4,148.7,144.4,143.4,141.8,136.2,133.9,132.8,132.1,130.5,130.2,129.9,129.1,129.0,128.7,128.4,128.2,127.2,126.8,126.4,126.0,123.7,121.32,121.30,121.0,70.1.HRMS(ESI):Calcd.for[C32H21AuNO3]+664.1181,found 664.1164.
实施例18：金(III)络合物(S)-6的合成
具体操作参见实施例1，橙红色固体，收率90％。1H NMR(400MHz,CDCl3)δ9.33(d,J＝5.2Hz,1H),8.35(d,J＝7.6Hz,1H),8.23(td,J＝7.8,1.3Hz,1H),7.88(t,J＝6.0Hz,1H),7.74–7.61(m,3H),7.52(d,J＝7.8Hz,1H),7.42–7.31(m,2H),7.31–7.21(m,4H),7.17(d,J＝8.9Hz,1H),7.08(t,J＝7.6Hz,1H),7.03(t,J＝7.3Hz,1H),6.97(t,J＝7.0Hz,1H),6.44(d,J＝8.3Hz,1H),6.17(d,J＝9.9Hz,1H).13C NMR(101MHz,CDCl3)δ198.8,189.8,168.9,149.4,148.8,144.4,143.4,141.8,136.1,133.9,132.8,132.2,130.6,130.2,129.8,129.1,129.0,128.7,128.4,128.2,127.22,127.15,126.8,126.4,126.1,123.7,121.32,121.30,121.0,70.1.HRMS(ESI):Calcd.for[C32H21AuNO3]+664.1181,found 664.1175.
实施例19：金(III)络合物(R)-7的合成
具体操作参见实施例1，橙红色固体，收率87％。1H NMR(400MHz,CDCl3)δ8.89(dd,J＝6.1,1.7Hz,1H),8.08–7.97(m,1H),7.70(dd,J＝8.1,3.7Hz,2H),7.53(d,J＝7.7Hz,1H),7.49–7.37(m,4H),7.35(t,J＝7.4Hz,1H),7.31–7.25(m,2H),7.20(d,J＝8.9Hz,1H),7.17–7.09(m,2H),7.07–6.95(m,2H),6.88–6.78(m,1H),6.50(d,J＝8.3Hz,1H),6.27(d,J＝9.9Hz,1H),6.01(d,J＝8.0Hz,1H).13C NMR(101MHz,CDCl3)δ199.1,169.2,158.3,151.8,146.5,144.4,143.8,143.6,132.8,130.5,130.4,130.2,130.1,130.0,129.1,128.22,128.19,128.16,127.3,126.8,126.1,125.6,124.0,121.9,121.32,121.28,121.2,121.0,118.1,116.2,69.8.HRMS(ESI):Calcd.for[C31H21AuNO3]+652.1181,found 652.1161.
实施例20：金(III)络合物(S)-7的合成
具体操作参见实施例1，橙红色固体，收率85％。1H NMR(400MHz,CDCl3)δ8.88(dd,J＝6.1,1.8Hz,1H),8.02(td,J＝8.3,1.8Hz,1H),7.70(dd,J＝8.2,4.2Hz,2H),7.53(d,J＝7.6Hz,1H),7.49–7.37(m,4H),7.37–7.32(m,1H),7.31–7.25(m,2H),7.20(d,J＝8.9Hz,1H),7.17–7.08(m,2H),7.07–7.01(m,1H),7.01–6.95(m,1H),6.88–6.77(m,1H),6.50(d,J＝8.3Hz,1H),6.27(d,J＝9.9Hz,1H),6.06–5.95(m,1H).13C NMR(101MHz,CDCl3)δ199.0,169.2,158.4,151.8,146.4,144.5,143.8,143.5,132.9,130.52,130.45,130.2,130.1,130.0,129.1,128.20,128.17,128.1,127.4,126.8,126.0,125.6,124.0,121.9,121.3,121.2,120.9,118.1,116.2,69.8.HRMS(ESI):Calcd.for[C31H21AuNO3]+652.1181,found652.1165.
实施例19：金(III)络合物(R)-8的合成
具体操作参见实施例1，黄色固体，收率84％。1H NMR(400MHz,CDCl3)δ8.92(s,1H),8.37(d,J＝5.3Hz,1H),7.77(d,J＝8.9Hz,1H),7.75–7.70(m,1H),7.60(d,J＝7.4Hz,1H),7.56–7.45(m,3H),7.43–7.32(m,3H),7.29(d,J＝8.9Hz,1H),7.11(d,J＝7.0Hz,1H),7.03(td,J＝12.8,6.3Hz,2H),6.97(t,J＝7.4Hz,1H),6.70(t,J＝6.4Hz,1H),6.58(t,J＝7.5Hz,1H),6.47(d,J＝7.9Hz,1H),6.30(d,J＝9.8Hz,1H),5.65(d,J＝7.8Hz,1H).13C NMR(101MHz,CDCl3)δ202.9,169.4,150.0,145.3,145.1,144.6,140.0,137.0,133.3,130.8,130.7,130.5,129.8,128.9,128.7,128.4,128.3,127.3,126.6,126.3,124.0,123.5,121.4,121.1,121.0,118.8,116.9,115.6,115.4,70.0.HRMS(ESI):Calcd.for[C31H22AuN2O2]+651.1341,found 651.1346.
实施例20：金(III)络合物(S)-8的合成
具体操作参见实施例1，黄色固体，收率80％。1H NMR(400MHz,CDCl3)δ8.92(s,1H),8.37(d,J＝5.2Hz,1H),7.77(d,J＝8.9Hz,1H),7.75–7.69(m,1H),7.60(d,J＝7.4Hz,1H),7.56–7.44(m,3H),7.43–7.32(m,3H),7.28(d,J＝8.9Hz,2H),7.11(d,J＝7.8Hz,1H),7.03(td,J＝12.8,6.2Hz,2H),6.96(t,J＝7.4Hz,1H),6.70(t,J＝6.5Hz,1H),6.58(t,J＝7.5Hz,1H),6.46(d,J＝7.9Hz,1H),6.30(d,J＝9.8Hz,1H),5.65(d,J＝7.8Hz,1H).13C NMR(100MHz,CDCl3):δ202.9,169.4,150.0,145.3,145.1,144.6,140.0,137.0,133.3,130.8,130.7,130.5,129.8,128.9,128.7,128.4,128.3,127.3,126.6,126.3,124.0,123.5,121.4,121.05,120.96,118.8,116.9,115.6,115.4,70.0.HRMS(ESI):Calcd.for[C31H22AuN2O2]+651.1341,found 651.1315.
实施例21：金(III)络合物(R)-9的合成
具体操作参见实施例1，橙红色固体，收率91％。1H NMR(400MHz,CDCl3)δ9.44(d,J＝5.0Hz,1H),8.04(td,J＝8.0,1.4Hz,1H),7.96(d,J＝9.9Hz,1H),7.85(d,J＝8.1Hz,1H),7.75–7.67(m,2H),7.54(t,J＝6.7Hz,3H),7.47(d,J＝7.8Hz,1H),7.28–7.18(m,4H),7.15–7.08(m,2H),7.07–6.99(m,2H),6.79(d,J＝7.6Hz,1H),6.67(d,J＝9.8Hz,1H).13C NMR(101MHz,CDCl3)δ200.8,168.4,162.4,147.5,147.2,145.0,143.7,142.6,141.7,133.3,131.2,130.9,130.6,130.5,130.3,129.22,129.16,128.9,128.6,128.2,127.3,126.4,126.3,126.0,124.7,123.3,121.7,120.9,120.8,119.8,68.5.HRMS(ESI):Calcd.for[C31H21AuNO2]+636.1232,found 636.1221.
实施例22：金(III)络合物(S)-9的合成
具体操作参见实施例1，橙红色固体，收率95％。1H NMR(400MHz,CDCl3)δ9.44(d,J＝5.0Hz,1H),8.04(td,J＝8.0,1.4Hz,1H),7.96(d,J＝9.9Hz,1H),7.85(d,J＝8.1Hz,1H),7.75–7.65(m,2H),7.54(t,J＝6.7Hz,3H),7.47(d,J＝7.8Hz,1H),7.28–7.17(m,4H),7.16–7.08(m,2H),7.07–6.98(m,2H),6.79(d,J＝7.4Hz,1H),6.67(d,J＝9.8Hz,1H).13C NMR(101MHz,CDCl3)δ200.8,168.4,162.3,147.5,147.2,145.0,143.7,142.5,141.8,133.3,131.2,130.9,130.6,130.5,130.3,129.21,129.16,128.9,128.7,128.2,127.3,126.5,126.3,126.1,124.8,123.3,121.7,120.9,120.8,119.8,68.5.HRMS(ESI):Calcd.for[C31H21AuNO2]+636.1232,found 636.1227.
实施例23：金(III)络合物(R)-10的合成
具体操作参见实施例1，橙红色固体，收率91％。1H NMR(400MHz,CDCl3)δ9.62(d,J＝4.9Hz,1H),8.51(d,J＝8.0Hz,1H),8.05(d,J＝10.0Hz,1H),7.87(dd,J＝8.0,5.0Hz,1H),7.81(d,J＝8.6Hz,1H),7.78–7.65(m,4H),7.60(d,J＝7.9Hz,1H),7.51(dt,J＝15.0,7.3Hz,3H),7.34(d,J＝8.7Hz,1H),7.21(t,J＝7.3Hz,1H),7.14–7.01(m,3H),6.83(d,J＝7.1Hz,1H),6.73(d,J＝10.0Hz,1H).13C NMR(101MHz,CDCl3)δ200.6,169.0,151.2,147.3,146.4,145.1,141.0,139.9,139.7,134.5,133.2,130.7,130.6,130.4,130.08,130.05,129.2,128.9,128.9,128.80,128.77,128.3,127.8,126.5,126.13,126.06,125.9,123.5,122.1,121.7,121.0,120.8,68.9.HRMS(ESI):Calcd.for[C33H21AuNO2]+660.1232,found660.1243.
实施例24：金(III)络合物(S)-10的合成
具体操作参见实施例1，橙红色固体，收率88％。1H NMR(400MHz,CDCl3)δ9.58(d,J＝4.4Hz,1H),8.49(d,J＝8.0Hz,1H),8.05(d,J＝9.9Hz,1H),7.85(dd,J＝8.0,5.2Hz,1H),7.80–7.71(m,3H),7.70(d,J＝7.6Hz,1H),7.66(d,J＝8.7Hz,1H),7.60(d,J＝7.5Hz,1H),7.55–7.44(m,3H),7.35(d,J＝8.8Hz,1H),7.21(t,J＝7.4Hz,1H),7.14–7.01(m,3H),6.83(d,J＝9.0Hz,1H),6.74(d,J＝9.9Hz,1H).13C NMR(101MHz,CDCl3)δ200.6,168.9,151.2,147.3,146.4,145.2,141.0,140.0,134.5,133.2,130.7,130.6,130.4,130.1,130.0,129.2,128.91,128.85,128.81,128.75,128.3,127.8,126.5,126.13,126.06,125.9,123.5,122.1,121.7,121.0,120.8,68.9.HRMS(ESI):Calcd.for[C33H21AuNO2]+660.1232,found 660.1211.
实施例25：金(III)络合物(R)-11的合成
具体操作参见实施例1，橙红色固体，收率83％。1H NMR(400MHz,CDCl3)δ10.02(s,1H),8.20(d,J＝8.4Hz,1H),8.17(s,1H),7.99(t,J＝7.9Hz,2H),7.92(t,J＝7.3Hz,1H),7.82–7.70(m,3H),7.64(d,J＝7.7Hz,1H),7.57(d,J＝7.8Hz,1H),7.50(d,J＝7.7Hz,1H),7.37(d,J＝8.8Hz,1H),7.26–7.18(m,3H),7.15–7.01(m,4H),6.83(d,J＝7.8Hz,1H),6.70(d,J＝9.8Hz,1H).13C NMR(101MHz,CDCl3):δ207.0,201.1,168.2,154.0,151.5,147.3,145.1,143.7,141.1,138.1,134.2,133.4,130.7,130.64,130.59,130.4,130.0,129.6,129.3,129.2,129.0,128.9,128.7,128.3,127.5,127.2,126.5,126.4,126.1,123.8,121.7,121.0,120.9,116.5,68.4.HRMS(ESI):Calcd.for[C35H23AuNO2]+686.1389,found686.1407.
实施例26：金(III)络合物(S)-11的合成
具体操作参见实施例1，橙红色固体，收率89％。1H NMR(400MHz,CDCl3)δ10.02(s,1H),8.20(d,J＝8.3Hz,1H),8.17(s,1H),7.99(t,J＝8.1Hz,2H),7.92(t,J＝7.2Hz,1H),7.81–7.69(m,3H),7.63(d,J＝7.6Hz,1H),7.56(d,J＝7.9Hz,1H),7.50(d,J＝7.8Hz,1H),7.36(d,J＝8.9Hz,1H),7.28–7.16(m,4H),7.15–7.01(m,4H),6.83(d,J＝7.3Hz,1H),6.69(d,J＝9.8Hz,1H).13C NMR(101MHz,CDCl3)δ201.0,168.3,154.1,151.5,147.3,145.0,143.7,141.2,138.1,134.2,133.4,130.8,130.7,130.6,130.3,130.0,129.6,129.3,129.2,128.92,128.88,128.6,128.2,127.5,127.4,127.2,126.5,126.4,126.1,123.8,121.7,121.0,120.9,116.5,68.5.HRMS(ESI):Calcd.for[C35H23AuNO2]+686.1389,found686.1371.
实施例27：金(III)络合物(R)-12的合成
具体操作参见实施例1，橙红色固体，收率77％。1H NMR(400MHz,CDCl3)δ7.92(s,1H),7.84–7.75(m,6H),7.61–7.55(m,1H),7.52–7.44(m,8H),7.43–7.35(m,11H),7.33(d,J＝7.4Hz,3H),7.26–7.16(m,11H),7.09(dd,J＝8.2,6.0Hz,1H),7.01(t,J＝6.9Hz,2H),4.26(d,J＝8.3Hz,1H),4.15(d,J＝8.3Hz,1H),0.65(s,6H).13C NMR(101MHz,CDCl3)δ201.9,176.5,174.9,156.6,148.1,142.4,140.1,137.4,136.7,136.34,136.28,134.7,134.1,133.1,130.8,130.5,130.22,130.16,129.5,129.1,129.0,128.71,128.69,127.9,127.6,127.4,126.75,126.72,126.5,126.0,124.6,121.2,120.5,84.2,70.6,66.7,25.7,25.3.HRMS(ESI):Calcd.for[C67H53AuNO3Si2]+1172.3224,found 1172.3246.
实施例28：金(III)络合物(S)-12的合成
具体操作参见实施例1，橙红色固体，收率72％。1H NMR(400MHz,CDCl3)δ7.90(s,1H),7.84–7.72(m,6H),7.60–7.53(m,1H),7.46(dd,J＝17.6,7.3Hz,8H),7.42–7.29(m,14H),7.26–7.13(m,11H),7.10–7.03(m,1H),6.99(t,J＝7.6Hz,2H),4.25(d,J＝8.3Hz,1H),4.14(d,J＝8.3Hz,1H),0.64(s,6H).13C NMR(101MHz,CDCl3)δ201.9,176.5,174.9,156.5,148.1,142.3,140.1,137.4,136.7,136.3,134.7,134.1,133.1,130.79,130.5,130.2,130.1,129.5,129.1,128.9,128.69,128.67,127.6,127.4,126.72,126.70,126.5,126.0,124.6,121.2,120.5,84.2,70.6,66.7,25.7,25.3.HRMS(ESI):Calcd.for[C67H53AuNO3Si2]+1172.3224,found 1172.3204.
实施例29：金(III)络合物(R)-13的合成
具体操作参见实施例1，橙红色固体，收率77％。1H NMR(400MHz,CDCl3)δ7.77(s,1H),7.61(d,J＝7.4Hz,1H),7.52(s,1H),7.43(t,J＝7.8Hz,2H),7.39(d,J＝7.8Hz,1H),7.32(dd,J＝7.2,1.6Hz,1H),7.23(td,J＝7.6,1.7Hz,1H),7.20–7.13(m,2H),7.09–6.91(m,3H),6.74(d,J＝8.3Hz,1H),4.61(d,J＝8.5Hz,1H),4.56(d,J＝8.5Hz,1H),2.54(s,3H),2.12(s,3H),1.86(s,6H).13C NMR(101MHz,CDCl3)δ200.7,177.3,169.9,146.6,141.6,141.0,136.4,133.7,131.8,130.2,129.74,129.70,129.5,129.3,129.1,127.8,127.6,127.4,126.5,126.4,124.9,124.4,120.5,120.3,84.6,70.1,67.3,27.2,26.9,17.1,16.4.HRMS(ESI):Calcd.for[C33H29AuNO3]+684.1807,found 684.1783.
实施例30：金(III)络合物(S)-13的合成
具体操作参见实施例1，橙红色固体，收率83％。1H NMR(400MHz,CDCl3)δ7.77(s,1H),7.61(d,J＝7.6Hz,1H),7.51(s,1H),7.42(t,J＝8.5Hz,2H),7.38(d,J＝7.7Hz,1H),7.32(dd,J＝7.2,1.5Hz,1H),7.26–7.13(m,3H),7.09–6.89(m,3H),6.73(d,J＝8.3Hz,1H),4.62(d,J＝8.5Hz,1H),4.57(d,J＝8.5Hz,1H),2.53(s,3H),2.11(s,3H),1.86(s,6H).13CNMR(101MHz,CDCl3)δ200.7,177.3,170.0,146.6,141.6,141.0,136.4,133.7,131.8,130.2,129.7,129.5,129.3,129.1,127.8,127.6,127.4,126.5,126.4,124.9,124.4,120.5,120.3,84.6,70.1,67.3,27.2,26.9,17.1,16.4.HRMS(ESI):Calcd.for[C33H29AuNO3]+684.1807,found 684.1811.
实施例31：金(III)络合物(R)-14的合成
具体操作参见实施例1，橙红色固体，收率93％。1H NMR(400MHz,CDCl3)δ7.84(d,J＝10.9Hz,2H),7.67(s,1H),7.57(d,J＝8.8Hz,1H),7.39–7.15(m,7H),7.10(d,J＝8.6Hz,1H),6.66(d,J＝9.8Hz,1H),6.57(d,J＝8.9Hz,1H),4.63(d,J＝8.4Hz,1H),4.58(d,J＝8.4Hz,1H),1.82(s,6H).13C NMR(101MHz,CDCl3)δ200.1,177.4,171.4,145.8,143.4,139.8,133.9,133.3,132.0,131.1,131.0,130.4,130.20,130.16,130.0,129.7,129.5,129.2,128.0,126.9,124.8,123.1,122.2,120.1,114.2,84.7,69.4,67.5,27.2,26.9.HRMS(ESI):Calcd.for[C31H23Br2AuNO3]+811.9705,found 811.9655.
实施例32：金(III)络合物(S)-14的合成
具体操作参见实施例1，橙红色固体，收率89％。1H NMR(400MHz,CDCl3)δ7.83(dd,J＝7.3,6.2Hz,2H),7.66(d,J＝1.8Hz,1H),7.57(d,J＝8.9Hz,1H),7.34(dd,J＝6.1,1.6Hz,1H),7.31–7.19(m,6H),7.17(d,J＝8.9Hz,1H),7.10(dd,J＝9.0,2.0Hz,1H),6.66(d,J＝9.9Hz,1H),6.57(d,J＝9.0Hz,1H),4.61(dd,J＝19.3,8.5Hz,2H),1.83(s,6H).13C NMR(101MHz,CDCl3)δ200.1,177.4,171.4,145.8,143.4,139.9,133.9,133.3,132.0,131.1,131.0,130.4,130.20,130.16,130.0,129.7,129.5,129.2,127.9,126.9,124.7,123.1,122.2,120.1,114.2,84.7,69.5,67.5,27.2,26.9.HRMS(ESI):Calcd.for[C31H23Br2AuNO3]+811.9705,found 811.9677.
实施例33：金(III)络合物(R)-15的合成
具体操作参见实施例1，橙红色固体，收率83％。1H NMR(400MHz,CDCl3)δ8.19(s,1H),8.13(s,1H),8.09–8.03(m,3H),7.99(dd,J＝7.9,5.5Hz,2H),7.95–7.84(m,8H),7.82–7.66(m,6H),7.66–7.59(m,3H),7.58–7.48(m,4H),7.37–7.24(m,3H),7.20(dd,J＝8.0,6.7Hz,2H),7.14–7.03(m,3H),4.52(d,J＝8.5Hz,1H),4.44(d,J＝8.5Hz,1H),1.64(s,3H),1.63(s,3H).13C NMR(101MHz,CDCl3)δ198.8,177.3,168.6,146.9,142.9,140.8,140.5,139.1,138.9,138.8,138.5,138.3,135.5,133.8,133.7,133.6,133.5,132.7,132.64,132.61,130.8,130.4,130.12,130.1,129.8,129.7,129.6,129.2,129.0,128.6,128.4,128.24,128.20,127.74,127.71,127.6,127.0,126.8,126.5,126.4,126.33,126.29,126.2,126.0,125.9,125.73,125.68,125.53,125.52,121.1,120.5,84.5,70.8,67.1,27.1,26.6.HRMS(ESI):Calcd.for[C63H45AuNO3]+1060.3059,found 1060.3013.
实施例34：(O^C,C^N)-Au(III)络合物(S)-13的合成
具体操作参见实施例1，橙红色固体，收率87％。1H NMR(400MHz,CDCl3)δ8.18(s,1H),8.13(s,1H),8.09–8.03(m,3H),7.99(t,J＝6.6Hz,2H),7.96–7.83(m,8H),7.81–7.67(m,6H),7.66–7.47(m,7H),7.37–7.23(m,3H),7.20(t,J＝7.2Hz,2H),7.14–7.03(m,3H),4.53(d,J＝8.5Hz,1H),4.44(d,J＝8.5Hz,1H),1.63(s,6H).13C NMR(101MHz,CDCl3)δ198.8,177.3,168.6,146.9,143.0,140.8,139.1,138.9,138.8,138.5,138.3,135.5,133.8,133.7,133.6,133.5,132.66,132.64,132.61,130.8,130.4,130.2,130.1,129.8,129.7,129.6,129.2,129.0,128.6,128.4,128.24,128.21,127.75,127.71,127.65,127.0,126.8,126.5,126.4,126.34,126.30,126.2,126.0,125.9,125.73,125.69,125.54,125.52,121.1,120.5,84.5,70.7,67.1,27.1,26.6.HRMS(ESI):Calcd.for[C63H45AuNO3]+1060.3059,found 1060.3091.
实施例35：金(III)络合物(R)-16的合成
具体操作参见实施例1，橙红色固体，收率85％。1H NMR(400MHz,CDCl3)δ8.01(s,1H),7.77–7.67(m,2H),7.58(d,J＝7.6Hz,2H),7.54(d,J＝7.7Hz,1H),7.50(s,2H),7.33–7.27(m,3H),7.26–7.11(m,5H),7.09–6.99(m,4H),6.97(s,1H),4.54(d,J＝8.5Hz,1H),4.45(d,J＝8.5Hz,1H),2.43(s,6H),2.31(s,6H),1.62(s,3H),1.59(s,3H).13C NMR(101MHz,CDCl3)δ198.9,177.2,168.6,146.8,142.8,140.7,139.6,139.1,137.4,136.7,136.2,134.3,133.5,132.5,130.3,130.2,129.9,129.84,129.78,129.8,129.7,129.6,129.4,128.8,128.4,128.1,128.0,127.6,126.9,126.6,126.3,125.9,120.9,120.5,84.3,70.7,67.1,27.1,26.2,21.5,21.3.HRMS(ESI):Calcd.for[C47H41AuNO3]+864.2746,found864.2715.
实施例36：金(III)络合物(S)-16的合成
具体操作参见实施例1，橙红色固体，收率88％。1H NMR(400MHz,CDCl3)δ8.02(s,1H),7.77–7.67(m,2H),7.62–7.56(m,2H),7.54(d,J＝7.8Hz,1H),7.51(s,2H),7.35–7.27(m,2H),7.27–7.12(m,5H),7.10–7.00(m,4H),6.98(s,1H),4.54(d,J＝8.5Hz,1H),4.44(d,J＝8.5Hz,1H),2.44(s,6H),2.32(s,6H),1.62(d,J＝3.2Hz,3H),1.59(s,3H).13C NMR(101MHz,CDCl3)δ198.9,177.3,168.7,146.9,142.8,140.7,139.6,139.1,137.4,136.7,136.3,134.3,133.5,132.5,130.4,130.2,129.9,129.85,129.79,129.7,129.6,129.4,128.8,128.4,128.1,128.0,127.6,126.9,126.6,126.3,125.9,120.9,120.5,84.4,70.7,67.1,27.1,26.2,21.5,21.3.HRMS(ESI):Calcd.for[C47H41AuNO3]+864.2746,found864.2720.
实施例37：金(III)络合物(R)-17的合成
具体操作参见实施例1，橙红色固体，收率73％。1H NMR(400MHz,CDCl3):δ8.33(s,2H),8.16(s,1H),7.98(s,2H),7.91(s,1H),7.84(s,1H),7.81–7.75(m,1H),7.74(s,1H),7.70(d,J＝7.4Hz,1H),7.58(d,J＝7.6Hz,1H),7.42(d,J＝7.7Hz,1H),7.37–7.21(m,5H),7.16–7.06(m,2H),6.96–6.86(m,1H),4.55(d,J＝8.5Hz,1H),4.49(d,J＝8.5Hz,1H),1.52(s,6H).13C NMR(101MHz,CDCl3):δ197.8,177.3,168.0,147.0,144.5,142.0,139.3,138.2,135.9,133.4,133.04,131.5,131.3,131.2,131.1,130.8,130.4,130.2,129.7,129.5,129.3,129.2,128.8,128.6,128.1,127.22,127.19,127.1,126.3,125.1,124.7,122.4,122.0,121.7,120.5,120.3,84.5,70.4,67.2,26.8,26.4.19F NMR(376MHz,CDCl3):δ-62.2,-62.7.HRMS(ESI):Calcd.for[C47H29AuF12NO3]+1080.1616,found 1080.1621.
实施例38：金(III)络合物(S)-17的合成
具体操作参见实施例1，橙红色固体，收率80％。1H NMR(400MHz,CDCl3)δ8.32(s,2H),8.15(s,1H),7.97(s,2H),7.90(s,1H),7.83(s,1H),7.80–7.75(m,1H),7.73(s,1H),7.69(d,J＝7.2Hz,1H),7.57(d,J＝7.6Hz,1H),7.41(d,J＝7.6Hz,1H),7.37–7.20(m,5H),7.16–7.05(m,2H),6.95–6.86(m,1H),4.55(d,J＝8.5Hz,1H),4.49(d,J＝8.5Hz,1H),1.52(s,6H).13C NMR(101MHz,CDCl3)δ197.8,177.3,167.9,147.0,144.5,142.0,139.3,138.2,135.9,133.4,133.0,131.5,131.3,131.2,131.1,130.8,130.4,130.1,129.7,129.5,129.3,129.2,128.9,128.6,128.1,127.22,127.18,127.1,126.3,125.1,124.7,122.4,121.9,121.7,120.5,120.2,84.5,77.4,67.2,26.8,26.4.19F NMR(376MHz,CDCl3):δ-62.2,-62.7.HRMS(ESI):Calcd.for[C47H29AuF12NO3]+1080.1616,found 1080.1606.
实施例39：金(III)络合物(R)-18的合成
具体操作参见实施例1，橙红色固体，收率78％。1H NMR(400MHz,CDCl3)δ8.48(s,1H),8.43(s,1H),8.23(d,J＝8.8Hz,1H),8.09(t,J＝7.5Hz,2H),8.04(s,1H),7.99(d,J＝8.5Hz,2H),7.94(dd,J＝8.5,4.8Hz,2H),7.86–7.76(m,3H),7.68(d,J＝7.0Hz,1H),7.63(d,J＝8.9Hz,1H),7.53–7.12(m,16H),6.67–6.54(m,1H),4.19(d,J＝8.5Hz,1H),4.11(d,J＝8.5Hz,1H),0.46(s,3H),0.39(s,3H).13C NMR(101MHz,CDCl3)δ198.2,176.6,170.3,147.4,146.7,140.5,137.4,135.0,133.6,133.5,131.9,131.6,131.5,131.2,131.14,131.06,130.8,130.7,130.6,130.5,130.4,130.1,129.5,129.1,128.7,128.5,128.34,128.31,128.2,127.8,127.6,127.4,127.14,127.06,127.0,126.9,126.7,126.0,125.8,125.5,125.2,125.0,124.9,124.83,124.80,124.74,124.66,121.3,121.1,84.5,71.1,66.9,25.4,24.9.HRMS(ESI):Calcd.for[C59H41AuNO3]+1008.2746,found 1008.2732.
实施例40：金(III)络合物(S)-18的合成
具体操作参见实施例1，橙红色固体，收率74％。1H NMR(400MHz,CDCl3)δ8.48(s,1H),8.42(s,1H),8.22(d,J＝8.8Hz,1H),8.08(dd,J＝8.1,4.8Hz,2H),8.04(s,1H),7.99(d,J＝8.5Hz,2H),7.93(d,J＝8.1Hz,2H),7.84–7.76(m,3H),7.68(d,J＝7.2Hz,1H),7.62(d,J＝8.9Hz,1H),7.52–7.13(m,16H),6.66–6.54(m,1H),4.19(d,J＝8.5Hz,1H),4.12(d,J＝8.5Hz,1H),0.46(s,3H),0.39(s,3H).13C NMR(101MHz,CDCl3)δ198.2,176.6,170.3,147.4,146.7,140.5,137.4,135.0,133.5,133.4,131.9,131.6,131.5,131.2,131.1,131.0,130.8,130.7,130.6,130.5,130.4,130.1,129.5,129.1,128.7,128.4,128.33,128.29,128.2,127.8,127.6,127.4,127.1,127.04,126.96,126.9,126.6,126.0,125.8,125.5,125.2,125.0,124.9,124.81,124.79,124.7,124.6,121.3,121.1,84.5,71.1,66.9,25.4,24.9.HRMS(ESI):Calcd.for[C59H41AuNO3]+1008.2746,found 1008.2737.
实施例41：金(III)络合物(R)-19的合成
具体操作参见实施例1，橙红色固体，收率91％。1H NMR(400MHz,CDCl3)δ8.33(d,J＝8.7Hz,2H),8.19(d,J＝8.8Hz,2H),8.14(s,1H),8.08(d,J＝8.7Hz,2H),7.82–7.72(m,2H),7.67(d,J＝8.8Hz,3H),7.56(d,J＝7.6Hz,1H),7.44(d,J＝7.7Hz,1H),7.38–7.19(m,5H),7.15–7.02(m,2H),6.97–6.87(m,1H),4.57(d,J＝8.6Hz,1H),4.51(d,J＝8.6Hz,1H),1.59(s,3H),1.56(s,3H).13C NMR(101MHz,CDCl3)δ197.9,177.3,168.1,147.4,147.0,146.8,146.5,144.6,143.0,139.6,136.8,133.6,133.1,131.6,131.1,130.88,130.85,130.4,129.9,129.7,129.5,129.3,129.1,129.0,128.6,128.1,127.1,127.0,126.6,123.2,122.9,121.6,120.3,84.5,70.5,67.1,27.0,26.6.HRMS(ESI):Calcd.for[C43H31AuN3O7]+898.1822,found 898.1807.
实施例42：金(III)络合物(R)-20的合成
具体操作参见实施例1，橙红色固体，收率87％。1H NMR(400MHz,CDCl3)δ8.08(s,1H),7.99(d,J＝8.0Hz,2H),7.78–7.68(m,4H),7.66–7.53(m,6H),7.49(d,J＝7.7Hz,1H),7.35–7.25(m,3H),7.21(t,J＝7.3Hz,2H),7.12–7.02(m,2H),6.98–6.91(m,1H),4.55(d,J＝8.5Hz,1H),4.48(d,J＝8.5Hz,1H),1.54(s,3H),1.53(s,3H).13C NMR(101MHz,CDCl3)δ198.3,177.3,168.3,146.9,143.9,143.4,140.0,137.6,133.5,132.8,132.6,130.7,130.5,130.34,130.32,129.7,129.39,129.37,129.3,129.2,128.8,128.7,127.9,126.9,126.5,126.3,125.0,124.9(d,J＝3.7Hz),124.4(d,J＝3.7Hz),121.3,120.3,84.5,70.5,67.1,26.9,26.4.19F NMR(376MHz,CDCl3)δ-62.2,-62.6.HRMS(ESI):Calcd.for[C45H31AuF6NO3]+944.1868,found 944.1833.
实施例43：金(III)络合物(R)-21的合成
具体操作参见实施例1，橙红色固体，收率92％。1H NMR(400MHz,CDCl3)δ8.44(s,1H),7.99(s,1H),7.61(dd,J＝6.1,3.2Hz,1H),7.49(d,J＝7.0Hz,1H),7.42(d,J＝7.7Hz,1H),7.34(d,J＝7.1Hz,1H),7.24(ddd,J＝10.9,5.1,2.1Hz,4H),7.17(dd,J＝10.8,4.3Hz,1H),7.05(dq,J＝6.7,3.5Hz,2H),6.64(dd,J＝6.2,3.4Hz,1H),4.67(d,J＝8.5Hz,1H),4.60(d,J＝8.5Hz,1H),1.92(s,3H),1.89(s,3H).13C NMR(101MHz,CDCl3)δ192.4,177.4,166.5,146.5,146.1,139.3,134.0,132.5,132.0,130.7,130.3,129.7,129.5,128.90,128.87,128.1,128.0,127.5,127.03,126.96,126.6,125.6,125.4,121.6,120.3,116.8,84.7,67.6,27.3,26.8.HRMS(ESI):Calcd.for[C31H23AuBr2NO3]+811.9725,found811.9702.
实施例44：金(III)络合物(R)-22的合成
具体操作参见实施例1，橙红色固体，收率68％。1H NMR(400MHz,CDCl3)δ8.57(s,1H),8.42(s,1H),8.22–8.15(m,2H),8.15–8.10(m,2H),8.08(s,1H),8.02–7.90(m,3H),7.83(dd,J＝10.3,6.3Hz,2H),7.76–7.68(m,2H),7.67(s,1H),7.65(dd,J＝6.0,3.0Hz,1H),7.57–7.46(m,3H),7.44–7.25(m,10H),7.22–7.13(m,2H),6.83(dd,J＝8.1,7.2Hz,1H),6.68(t,J＝7.5Hz,1H),6.26(t,J＝7.8Hz,2H),5.99(d,J＝7.4Hz,2H),4.79(t,J＝9.4Hz,1H),4.69(dd,J＝9.1,4.9Hz,1H),4.30(dd,J＝9.8,4.8Hz,1H).13C NMR(101MHz,CDCl3)δ197.6,178.4,170.3,148.0,146.8,141.2,137.6,137.0,135.6,133.8,133.5,132.7,132.0,131.6,131.5,131.29,131.26,131.2,130.82,130.76,130.6,130.5,130.4,130.0,129.7,129.5,129.3,128.8,128.5,128.4,128.3,128.25,128.18,128.0,127.9,127.8,127.2,127.0,126.9,126.7,126.5,125.9,125.8,125.7,125.38,125.35,125.1,125.0,124.9,124.73,124.67,121.2,121.0,79.7,70.4,64.8.HRMS(ESI):Calcd.for[C63H41AuNO3]+1056.2746,found 1056.2681.
实施例45：金(III)络合物(R,S)-23的合成
具体操作参见实施例1，橙红色固体，收率64％。1H NMR(400MHz,CDCl3)δ7.77(s,1H),7.55(dd,J＝7.3,4.4Hz,2H),7.52–7.33(m,9H),7.33–7.26(m,2H),7.23(t,J＝7.2Hz,1H),7.13(t,J＝7.4Hz,1H),7.02(t,J＝7.5Hz,1H),6.98–6.88(m,2H),6.71(d,J＝8.2Hz,1H),5.67(dd,J＝10.0,7.0Hz,1H),5.22(t,J＝9.5Hz,1H),4.78(dd,J＝8.8,7.1Hz,1H),2.13(s,3H),2.11(s,3H).13C NMR(101MHz,CDCl3)δ200.7,179.7,169.3,146.5,142.0,141.7,138.5,136.6,134.3,131.6,130.4,130.3,129.4,129.21,129.16,129.1,129.0,128.9,127.89,127.87,127.3,126.9,126.6,126.3,124.9,124.6,120.5,120.1,80.1,69.4,66.2,16.6,16.5.HRMS(ESI):Calcd.for[C37H29AuNO3]+732.1807,found 732.1806.
实施例46：金(III)络合物(R,R)-23的合成
具体操作参见实施例1，橙红色固体，收率79％。1H NMR(400MHz,CDCl3)δ7.72(s,1H),7.55(d,J＝7.8Hz,1H),7.52–7.36(m,8H),7.28(d,J＝4.2Hz,2H),7.26–7.19(m,2H),7.15(t,J＝7.4Hz,1H),6.94(ddd,J＝23.0,14.8,7.2Hz,3H),6.63(d,J＝8.3Hz,1H),5.67(dd,J＝10.0,6.9Hz,1H),5.23(t,J＝9.5Hz,1H),4.85(dd,J＝8.8,7.0Hz,1H),2.26(s,3H),2.07(s,3H).13C NMR(101MHz,CDCl3)δ200.3,179.5,169.7,146.3,141.5,141.4,138.8,136.2,133.9,131.8,130.4,130.2,129.6,129.44,129.36,129.3,129.1,129.0,128.9,128.8,127.8,127.6,127.3,127.2,126.6,126.4,124.8,124.3,120.4,120.2,79.9,69.7,66.0,16.9,16.4.HRMS(ESI):Calcd.for[C37H29AuNO3]+732.1807,found 732.1780.
实施例47：金(III)络合物(S,S)-24的合成
具体操作参见实施例1，橙红色固体，收率74％。1H NMR(400MHz,CDCl3)δ7.72(s,1H),7.55(d,J＝7.7Hz,1H),7.45(ddd,J＝15.1,13.3,5.3Hz,8H),7.28(d,J＝4.9Hz,2H),7.25–7.19(m,2H),7.15(t,J＝7.4Hz,1H),7.01–6.92(m,2H),6.89(t,J＝7.0Hz,1H),6.62(d,J＝8.3Hz,1H),5.67(dd,J＝10.0,6.9Hz,1H),5.24(t,J＝9.6Hz,1H),4.85(dd,J＝8.9,6.9Hz,1H),2.26(s,3H),2.06(s,3H).13C NMR(101MHz,CDCl3)δ200.3,179.5,169.7,146.3,141.5,141.4,138.8,136.2,133.9,131.8,130.4,130.2,129.6,129.44,129.37,129.3,129.1,129.0,128.9,128.8,127.8,127.6,127.3,127.2,126.6,126.4,124.8,124.3,120.4,120.2,79.9,69.7,66.0,16.9,16.4.HRMS(ESI):Calcd.for[C37H29AuNO3]+732.1807,found 732.1800.
实施例48：金(III)络合物(S,R)-23的合成
具体操作参见实施例1，橙红色固体，收率68％。1H NMR(400MHz,CDCl3)δ7.77(s,1H),7.55(t,J＝7.5Hz,2H),7.51–7.37(m,9H),7.32–7.26(m,1H),7.23(t,J＝7.1Hz,1H),7.13(t,J＝7.4Hz,1H),7.01(t,J＝7.5Hz,1H),6.98–6.87(m,2H),6.71(d,J＝8.2Hz,1H),5.68(dd,J＝10.0,7.0Hz,1H),5.23(t,J＝9.5Hz,1H),4.78(dd,J＝8.8,7.1Hz,1H),2.13(s,3H),2.11(s,3H).13C NMR(101MHz,CDCl3)δ200.7,179.7,169.3,146.6,142.0,141.6,138.5,136.7,134.3,131.6,130.5,130.3,129.4,129.2,129.15,129.13,129.0,128.89,127.88,127.86,127.3,126.9,126.6,126.3,124.8,124.6,120.5,120.1,80.1,69.4,66.2,16.6,16.5.HRMS(ESI):Calcd.for[C37H29AuNO3]+732.1807,found 732.1805.
实施例49：金(III)络合物(R,R)-24的合成
具体操作参见实施例1，橙红色固体，收率85％。1H NMR(400MHz,CDCl3):δ8.03(s,1H),7.76(d,J＝8.0Hz,1H),7.71-7.69(m,1H),7.65(s,1H),7.56(t,J＝8.4Hz,2H),7.42-7.34(m,4H),7.24-6.98(m,15H),5.40(dd,J＝4.4,9.6Hz,1H),5.10(t,J＝9.2Hz,1H),4.99(dd,J＝4.4,8.8Hz,1H),2.46(s,6H),2.32(s,6H).13C NMR(101MHz,CDCl3)δ198.3,178.7,168.5,146.5,142.5,141.3,140.1,138.8,138.5,137.3,136.8,136.3,134.3,133.7,132.5,130.2,130.0,129.9,129.7,129.6,129.43,129.41,129.3,128.8,128.7,128.6,128.3,128.1,128.0,127.8,127.3,126.8,126.7,126.6,125.84,125.80,120.77,120.4,79.7,70.7,65.5,21.6,21.3.HRMS(ESI):Calcd.for[C51H41AuNO3]+912.2746,found912.2743.
实施例50：金(III)络合物(S,S)-24的合成
具体操作参见实施例1，橙红色固体，收率87％。1H NMR(400MHz,CDCl3)δ7.97(s,1H),7.72–7.66(m,1H),7.65(s,1H),7.57(d,J＝7.6Hz,1H),7.50(s,2H),7.43(d,J＝7.7Hz,2H),7.34–7.27(m,2H),7.23(dt,J＝13.7,6.8Hz,3H),7.15–6.95(m,11H),6.83(d,J＝7.5Hz,1H),5.39(dd,J＝9.7,4.7Hz,1H),5.18(t,J＝9.4Hz,1H),5.00(dd,J＝9.0,4.7Hz,1H),2.47(d,J＝14.3Hz,6H),2.30(s,6H).13C NMR(101MHz,CDCl3)δ198.3,178.7,168.5,146.5,142.5,141.3,140.1,138.9,138.5,137.4,136.8,136.3,134.3,133.7,132.6,130.2,130.0,129.9,129.7,129.6,129.43,129.42,129.3,128.8,128.7,128.6,128.3,128.1,128.0,127.8,127.3,126.8,126.7,126.6,125.9,125.8,120.8,120.4,79.8,70.7,65.5,21.6,21.3.HRMS(ESI):Calcd.for[C51H41AuNO3]+912.2746,found 912.2759.
实施例51：金(III)络合物(S,R)-24的合成
具体操作参见实施例1，橙红色固体，收率80％。1H NMR(400MHz,CDCl3)δ8.03(s,1H),7.76(d,J＝7.8Hz,1H),7.73–7.67(m,1H),7.65(s,1H),7.56(t,J＝8.3Hz,2H),7.46–7.32(m,4H),7.26–6.97(m,15H),5.40(dd,J＝9.4,4.3Hz,1H),5.10(t,J＝9.2Hz,1H),4.99(dd,J＝8.9,4.3Hz,1H),2.46(s,6H),2.32(s,6H).13C NMR(101MHz,CDCl3)δ198.8,178.9,168.2,146.9,142.8,142.1,140.0,139.1,138.1,137.6,136.8,136.3,134.3,134.1,132.5,130.6,130.19,130.16,129.9,129.8,129.5,129.0,128.9,128.8,128.5,128.4,128.12,128.05,127.8,126.89,126.87,126.6,126.5,125.9,120.9,120.3,79.7,69.9,65.4,21.6,21.3.HRMS(ESI):Calcd.for[C51H41AuNO3]+912.2746,found 912.2739.
实施例52：消旋金(III)络合物(rac)-1的克级大量合成
将无光学活性的(rac)-1,1’-联萘酚(11.0mmol，3.15g)，无水碳酸铯(22.0mmol，7.15g)以及甲醇(140mL)置于250mL的圆底烧瓶中。室温下搅拌，慢慢加入基于噁唑啉配体骨架的2-[2’-(4’,4’-二甲基)噁唑啉基]苯基二氯化金(10.0mmol，4.41g)，观察到慢慢有橙红色沉淀产生。反应3小时后，过滤，所得橙红色固体用适量甲醇洗涤，得到橙红色固体(rac)-1(6.20g，
收率95％)。
实施例53：不添加共催化剂的情况下，稳定手性金(III)络合物I或II在催化2-炔基苯甲醛与原甲酸三酯的半缩醛化-环异构化串联反应中的应用。
其中[Au]为：
在20mL反应瓶中，加入2-炔基苯甲醛(0.5mmol)、原甲酸三酯(3.0mmol)、金(III)络合物rac-1(0.0125mmol)及DCE(2.0mL)，在室温或60℃的反应条件下，搅拌反应8-24小时，TLC检测反应完全后，旋转蒸发仪减压除去溶剂，硅胶柱层析，得到相应的六元环环化产物，所得结果见表1.
表1.不添加共催化剂的情况下，金(III)络合物I或II催化2-炔基苯甲醛化合物与原甲酸三酯的半缩醛化-环异构化反应
实施例54：添加共催化剂的情况下，稳定手性金(III)络合物I或II在催化2-炔基苯甲醛与原甲酸三酯的缩醛化-环异构化串联反应中的应用。
其中[Au]为：
在20mL反应瓶中，加入2-炔基苯甲醛(0.5mmol)、原甲酸三酯(3.0mmol)、金(III)络合物rac-1(0.0125mmol)、D(+)-10-樟脑磺酸(0.1mmol)及DCE(2.0mL)，在室温下搅拌反应24小时，TLC检测反应完全后，加水(0.2mL)继续搅拌半小时，旋转蒸发仪减压除去溶剂，硅胶柱层析，得到相应的五元环环化产物，所得结果见表2。
表2.添加共催化剂的情况下，金(III)络合物催化2-炔基苯甲醛化合物与原甲酸三酯的缩醛化-环异构化反应
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (11)
1.一种手性三价金络合物，其特征在于，所述手性三价金络合物由两个碳-金共价键、一个氧-金共价键以及一个氮-金配位键构成，具有手性联萘酚和噁唑啉配体骨架，或具有手性联萘酚和邻位取代吡啶配体骨架，所述手性三价金络合物具有下述通式I或通式II的化合物，以及所述通式I或通式II的消旋体和旋光异构体，
其中，R1、R2分别独立选自H、卤素、C1～C10的烃基、杂芳基，所述杂芳基为呋喃基、噻吩基或吡啶基，所述n的取值范围满足0≤n≤2，且R1、R2相同或不同；
R3、R4分别独立选自H、卤素、C1～C10的烃基、杂芳基，所述杂芳基为呋喃基、噻吩基或吡啶基；所述m的取值范围满足0≤m≤4，且R3、R4相同或不同；
R5选自H、卤素、C1～C10的烃基、杂芳基，所述杂芳基为呋喃基、噻吩基或吡啶基；所述o的取值范围满足0≤o≤4；
R6、R7分别独立选自H、C1～C10的烃基、杂芳基，所述杂芳基为呋喃基、噻吩基或吡啶基；或R6、R7为通过C2～C4的碳链，含氮、氧、硫的碳链连接成环；R6、R7相同或不同；
R8、R9分别独立选自H、卤素、C1～C10的烃基、杂芳基，所述杂芳基为呋喃基、噻吩基或吡啶基；所述p的取值范围满足0≤p≤4，所述q的取值范围满足0≤q≤4，R8、R9相同或不同；
X为CH2、NH、O、C＝O或者不含任何原子。
2.如权利要求1所述的手性三价金络合物，其特征在于，所述n＝2时，两个相邻的R1、R2同为C3～C7脂肪环或芳香环；和/或
所述m≥2时，两个相邻的R3、R4同为C3～C7脂肪环或芳香环；和/或
所述o≥2时，两个相邻的R5同为C3～C7脂肪环或芳香环；和/或
所述p≥2时，两个相邻的R8同为C3～C7脂肪环或芳香环；和/或
所述q≥2时，两个相邻的R9同为C3～C7脂肪环或芳香环；和/或
所述X不含原子时，相邻的R8、R9同为芳香环。
3.一种手性三价金络合物，其特征在于，包括下述结构的化合物，下述结构化合物的对映体、消旋体和非对映异构体，
4.一种手性三价金络合物，其特征在于，所述手性三价金络合物由两个碳-金共价键、一个氧-金共价键以及一个氮-金配位键构成，具有手性联萘酚和噁唑啉配体骨架，或具有手性联萘酚和邻位取代吡啶配体骨架，所述手性三价金络合物具有下述通式I或通式II的化合物，以及所述通式I或通式II的消旋体和旋光异构体，
其中，R1、R2分别独立选自H、卤素、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基，所述n的取值范围满足0≤n≤2，且R1、R2相同或不同；
R3、R4分别独立选自H、卤素、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；所述m的取值范围满足0≤m≤4，且R3、R4相同或不同；
R5选自H、卤素、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；所述o的取值范围满足0≤o≤4；
R6、R7分别独立选自H、苯基、取代苯基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；或R6、R7为通过C2～C4的碳链，含氮、氧、硫的碳链连接成环；R6、R7相同或不同；
R8、R9分别独立选自H、卤素、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基的取代基为C1～C10的烃基、烷氧基，取代基数量为1～5，所述杂芳基为呋喃基、噻吩基或吡啶基；所述p的取值范围满足0≤p≤4，所述q的取值范围满足0≤q≤4，R8、R9相同或不同；
X为CH2、NH、O、C＝O或者不含任何原子。
5.一种如权利要求1至4任一项所述手性三价金络合物的制备方法，包括以下步骤：
提供消旋的或具有旋光活性的如式1所述结构的联萘酚衍生物、如式2所述结构的噁唑啉-金(III)二氯化物或如式3所述结构的2-取代吡啶-金(III)二氯化物；
将所述联萘酚衍生物、噁唑啉-金(III)二氯化物或2-取代吡啶-金(III)二氯化物溶于有机溶剂中，在碱存在条件下发生如下化学反应，得到手性三价金络合物，其反应通式如下：
6.如权利要求5所述的手性三价金络合物的制备方法，其特征在于，所述1,1’-联萘酚衍生物为R-构型，式I或式II结构中与Au原子相连的手性碳是S-构型；
所述1,1’-联萘酚衍生物(式1)为S-构型，式I或式II中与Au原子相连的手性碳是R-构型。
7.如权利要求5所述的手性三价金络合物的制备方法，其特征在于，所述联萘酚衍生物、所述噁唑啉-金(III)二氯化物或2-取代吡啶-金(III)二氯化物、所述碱的摩尔比为0.90～1.25：1：1.80～2.50或1.0：0.9～1.25：2.0。
8.如权利要求5所述的手性三价金络合物的制备方法，其特征在于，所述有机溶剂为甲醇、乙醇、丙醇、异丙醇、丁醇、四氢呋喃、甲苯、二氧六环，二氯甲烷、氯仿、DCE中的至少一种；和/或
所述碱选自有机碱和无机碱中的一种，所述有机碱选自三乙胺、三丁胺、N-甲基吗啡啉、N,N-二乙基异丙胺、1,4-二氮杂二环[2.2.2]辛烷，所述无机碱选自碳酸钠，碳酸钾，碳酸铯，甲醇钠，叔丁醇钾。
9.一种如权利要求1-4任一所述手性三价金络合物的用途，其特征在于，所述手性三价金络合物用于催化2-炔基苯甲醛与原甲酸三酯的反应。
10.如权利要求9所述手性三价金络合物的用途，其特征在于，所述手性三价金络合物用于2-炔基苯甲醛与原甲酸三酯的缩醛化-环异构化串联反应或半缩醛化-环异构化串联反应。
11.一种如权利要求10所述手性三价金络合物的用途，其特征在于，所述原甲酸三酯包括原甲酸三甲酯、原甲酸三乙酯、原甲酸三丙酯、原甲酸三异丙酯和原甲酸三丁酯；和/或
用于所述缩醛化-环异构化串联反应或半缩醛化-环异构化串联反应的有机溶剂为乙腈、四氢呋喃、甲苯、二氧六环、二氯甲烷、氯仿、DCE中的至少一种。
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