CN112300214A - 钯复合物、其制备方法、轴手性联芳香化合物的制备方法 - Google Patents
钯复合物、其制备方法、轴手性联芳香化合物的制备方法 Download PDFInfo
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- CN112300214A CN112300214A CN201910681991.7A CN201910681991A CN112300214A CN 112300214 A CN112300214 A CN 112300214A CN 201910681991 A CN201910681991 A CN 201910681991A CN 112300214 A CN112300214 A CN 112300214A
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- -1 biaryl compound Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000002941 palladium compounds Chemical class 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 164
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000005859 coupling reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 62
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 39
- 229910052736 halogen Inorganic materials 0.000 claims description 37
- 150000002367 halogens Chemical class 0.000 claims description 37
- 239000013078 crystal Substances 0.000 claims description 33
- 125000005842 heteroatom Chemical group 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 125000001072 heteroaryl group Chemical group 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 20
- 125000006708 (C5-C14) heteroaryl group Chemical group 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 16
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 229910052794 bromium Inorganic materials 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 125000001624 naphthyl group Chemical group 0.000 claims description 13
- 125000004076 pyridyl group Chemical group 0.000 claims description 13
- 125000002950 monocyclic group Chemical group 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 229940125904 compound 1 Drugs 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 9
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 9
- 125000001544 thienyl group Chemical group 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 7
- 125000002541 furyl group Chemical group 0.000 claims description 7
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 125000001041 indolyl group Chemical group 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 4
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 4
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 4
- 239000012046 mixed solvent 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
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 claims description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004467 single crystal X-ray diffraction Methods 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 7
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 9
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 197
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 49
- 238000005160 1H NMR spectroscopy Methods 0.000 description 48
- 238000004128 high performance liquid chromatography Methods 0.000 description 39
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000007787 solid Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- 239000012230 colorless oil Substances 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000006069 Suzuki reaction reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XNIGURFWNPLWJM-UHFFFAOYSA-N 1-bromo-2-methoxynaphthalene Chemical compound C1=CC=CC2=C(Br)C(OC)=CC=C21 XNIGURFWNPLWJM-UHFFFAOYSA-N 0.000 description 4
- 150000001348 alkyl chlorides Chemical class 0.000 description 4
- 238000004296 chiral HPLC Methods 0.000 description 4
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MZRRSCBQKOOJCE-MELFUQDXSA-N CC1=CC(=C(C(=C1)[C@H](C)C2=CC(=CC(=C2)C(C)(C)C)C(C)(C)C)N(C3=C(C=C(C=C3[C@H](C)C4=CC(=CC(=C4)C(C)(C)C)C(C)(C)C)C)[C@H](C)C5=CC(=CC(=C5)C(C)(C)C)C(C)(C)C)C(=O)C(=O)N)[C@H](C)C6=CC(=CC(=C6)C(C)(C)C)C(C)(C)C Chemical compound CC1=CC(=C(C(=C1)[C@H](C)C2=CC(=CC(=C2)C(C)(C)C)C(C)(C)C)N(C3=C(C=C(C=C3[C@H](C)C4=CC(=CC(=C4)C(C)(C)C)C(C)(C)C)C)[C@H](C)C5=CC(=CC(=C5)C(C)(C)C)C(C)(C)C)C(=O)C(=O)N)[C@H](C)C6=CC(=CC(=C6)C(C)(C)C)C(C)(C)C MZRRSCBQKOOJCE-MELFUQDXSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001543 aryl boronic acids Chemical class 0.000 description 3
- 150000001499 aryl bromides Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000007429 general method Methods 0.000 description 3
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- NHVWTZOWDLOBBS-UHFFFAOYSA-N (2-methoxynaphthalen-1-yl)boronic acid Chemical compound C1=CC=CC2=C(B(O)O)C(OC)=CC=C21 NHVWTZOWDLOBBS-UHFFFAOYSA-N 0.000 description 2
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- IBGUDZMIAZLJNY-UHFFFAOYSA-N 1,4-dibromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=C(Br)C2=C1 IBGUDZMIAZLJNY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000005347 biaryls Chemical group 0.000 description 2
- SNQXJPARXFUULZ-UHFFFAOYSA-N dioxolane Chemical compound C1COOC1 SNQXJPARXFUULZ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RIZYBSMDFJDHOI-UHFFFAOYSA-N (2-methylnaphthalen-1-yl)boronic acid Chemical compound C1=CC=CC2=C(B(O)O)C(C)=CC=C21 RIZYBSMDFJDHOI-UHFFFAOYSA-N 0.000 description 1
- NSJVYHOPHZMZPN-UHFFFAOYSA-N (2-methylphenyl)boronic acid Chemical compound CC1=CC=CC=C1B(O)O NSJVYHOPHZMZPN-UHFFFAOYSA-N 0.000 description 1
- MLCJWRIUYXIWNU-OWOJBTEDSA-N (e)-ethene-1,2-diamine Chemical compound N\C=C\N MLCJWRIUYXIWNU-OWOJBTEDSA-N 0.000 description 1
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 1
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 1
- YWWZASFPWWPUBN-UHFFFAOYSA-N 1-bromoisoquinoline Chemical compound C1=CC=C2C(Br)=NC=CC2=C1 YWWZASFPWWPUBN-UHFFFAOYSA-N 0.000 description 1
- MTNQYTBSQXJOPN-CLJLJLNGSA-N 2,6-bis[(1R)-1-(3,5-ditert-butylphenyl)ethyl]-4-methylaniline Chemical compound C(C)(C)(C)C=1C=C(C=C(C=1)C(C)(C)C)[C@@H](C)C1=C(N)C(=CC(=C1)C)[C@H](C)C1=CC(=CC(=C1)C(C)(C)C)C(C)(C)C MTNQYTBSQXJOPN-CLJLJLNGSA-N 0.000 description 1
- RGFDVTUOFVOJKY-UHFFFAOYSA-N 2,6-bis[1-(3,5-ditert-butylphenyl)ethenyl]-4-methylaniline Chemical compound C(C)(C)(C)C=1C=C(C=C(C=1)C(C)(C)C)C(=C)C1=C(N)C(=CC(=C1)C)C(=C)C1=CC(=CC(=C1)C(C)(C)C)C(C)(C)C RGFDVTUOFVOJKY-UHFFFAOYSA-N 0.000 description 1
- ATDIROHVRVQMRO-UHFFFAOYSA-N 2,6-dibromo-4-methylaniline Chemical compound CC1=CC(Br)=C(N)C(Br)=C1 ATDIROHVRVQMRO-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- PWRBCZZQRRPXAB-UHFFFAOYSA-N 3-chloropyridine Chemical compound ClC1=CC=CN=C1 PWRBCZZQRRPXAB-UHFFFAOYSA-N 0.000 description 1
- GEFOXHSKBXZYNQ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-(2-methylnaphthalen-1-yl)-1,3,2-dioxaborolane Chemical compound CC1=CC=C2C=CC=CC2=C1B1OC(C)(C)C(C)(C)O1 GEFOXHSKBXZYNQ-UHFFFAOYSA-N 0.000 description 1
- NUFSJKMRPYGNHV-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-(2-methylphenyl)-1,3,2-dioxaborolane Chemical compound CC1=CC=CC=C1B1OC(C)(C)C(C)(C)O1 NUFSJKMRPYGNHV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
本发明提供了一种钯复合物、其制备方法、轴手性联芳香化合物的制备方法。本发明公开了如式IV或如式IV’所示化合物，钯复合物结构新颖，适用于偶联反应，合成的轴手性联芳香化合物结构多样，收率高，立体选择性好。本发明还公开了轴手性联芳香化合物的制备方法，该制备方法制得的轴手性联芳香化合物的收率高，反应立体选择性强，ee值可高达85％以上，绝大部分在90％以上，且底物适用性广，对杂环底物有很好的适用性，合成的轴手性联芳香化合物具有多种结构。
Description
技术领域
本发明涉及一种钯复合物、其制备方法、轴手性联芳香化合物的制备方法。
背景技术
轴手性联芳结构大量存在于天然产物和药物之中。特别是，在不对称催化领域中，常用的手性催化剂如联萘结构的手性二醇、含异喹啉结构的单膦配体等都具有轴手性联芳结构。在众多构建轴手性的方法中，钯催化的不对称Suzuki偶联认为是一类高效实用的方法，由于其原料易得并且对水氧都有很高的稳定性。在2000年，Buchwald课题组和Cammidge课题组同时报道了首例钯催化的不对称Suzuki偶联反应构建轴手性联芳基化合物，随后，有大量课题组相继在该领域进行拓展研究。a)Yin,J.J.；Buchwald,S.L.J.Am.Chem.Soc.2000,122,12051.b)Cammidge,A.N.；Crepy,K.V.L.2000,1723.c)Bermejo,A.；Ros,A.；Fernandez,R.；Lassaletta,J.M.J.Am.Chem.Soc.2008,130,15798.d)Uozumi,Y.；Matsuura,T.；Arakawa,T.；Yamada,Y.M.A.Angew.Chem.,Int.Ed.2009,48,2708.e)Yamamoto,T.；Akai,Y.；Nagata,Y.；Suginome,M.Angew.Chem.,Int.Ed.2011,50,8844.f)Xu,G.；Fu,W.；Liu,G.；Senanayake,C.H.；Tang,W.J.Am.Chem.Soc.2014,136,570.g)awai,K.；Tatumi,R.；Nakahodo,T.；Fujihara,H..Angew.Chem.,Int.Ed.2008,47,6917.尽管进行了大量的研究，目前仍然存在着几点急需解决的难题。第一点，含杂环底物由于其强配位能力、弱反应性、较差的稳定性以及较低的旋转能垒，导致这类底物很难构建轴手性产物；第二点，一个通用的能够兼容各种各样官能团的催化剂还未实现；第三点，构建邻位四取代联芳基化合物在不对称Suzuki偶联反应中仍然是一个难题；第四点，以往高对映选择性的实现往往依赖于邻位大位阻取代，这也同样限制了底物的范围；第五点，温和的反应条件和较低的催化剂用量仍然是追求的目标。第六点，高对应选择性的反应主要通过有限手性膦配体来实现，这也限制了该类反应的发展。我们设想利用强供电的氮杂环卡宾配体与钯形成复合物加速氧化加成以及抑制杂环底物配位毒化，目前手性氮杂环卡宾-钯复合物催化的不对称Suzuki反应最高ee值仅为80％，参见h)Benhamou,L.；Besnard,C.；Kundig,E.P.Organometallics.2014,33,260.我们发展了一系列手性氮杂环卡宾-钯复合物，开发手性氮杂环卡宾-钯复合物催化不对称Suzuki偶联反应合成轴手性联芳基化合物的高效合成方法，这将对天然产物合成、轴手性配体合成和新药设计都具有重要意义。
发明内容
本发明要解决的技术问题在于克服现有的钯催化的偶联反应构建轴手性联芳香化合物时，反应收率低，立体选择性差，底物结构单一等缺陷，而提供了一种钯复合物、其制备方法、轴手性联芳香化合物的制备方法。通过本发明的制备方法得到的联芳香化合物具有收率高、立体选择性好及结构多样等优势。
本发明通过以下技术方案解决上述技术问题。
本发明提供了一种如式IV或如式IV’所示化合物，其结构如下所示：
其中，Ar3a、Ar3b、Ar3c和Ar3d独立地为未取代或R3a-1取代的C6-C14的芳基；每个R3a-1独立地为C1-C4的烷基；
R7a、R7b、R7c、R8a、R8b和R8c独立地为氢或C1-C4的烷基；
R5和R6独立地为氢、C1-C4的烷基、卤素、
或C6-C10的芳基；其中，R5-1和R5-2独立地为氢或C1-C4的烷基；
为单键或双键；
或者，R5、R6和与其相连的碳原子一起形成
本发明一优选实施方案中，当Ar3a、Ar3b、Ar3c和Ar3d独立地为R3a-1取代的C6-C14的芳基时，所述的R3a-1可独立地为一个或多个，例如1、2、3或4个，当存在多个R3a-1时，所述的R3a-1可相同或不同。
本发明一优选实施方案中，当Ar3a、Ar3b、Ar3c和Ar3d独立地为未取代或R3a-1取代的C6-C14的芳基时，所述的C6-C14的芳基独立地为C6-C10的芳基，优选苯基或萘基，更优选苯基。
本发明一优选实施方案中，当R3a-1独立地为C1-C4的烷基时，所述的C1-C4的烷基独立地为甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基，优选甲基或叔丁基，更优选叔丁基。
本发明一优选实施方案中，当R7a、R7b、R7c、R8a、R8b和R8c独立地为C1-C4的烷基时，所述的C1-C4的烷基独立地为甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基，优选甲基。
本发明一优选实施方案中，当R5、R6、R5-1和R5-2独立地为C1-C4的烷基时，所述的C1-C4的烷基独立地为甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基。
本发明一优选实施方案中，当R5和R6独立地为卤素时，所述的卤素独立地为F、Cl、Br或I。
本发明一优选实施方案中，当R5和R6独立地为C6-C10的芳基时，所述的C6-C10的芳基独立地为苯基或萘基。
本发明一优选实施方案中，当Ar3a、Ar3b、Ar3c和Ar3d独立地为R3a-1取代的C6-C14的芳基时，所述的R3a-1取代的C6-C10的芳基独立地优选
本发明一优选实施方案中，所述的如式IV或如式IV’所示化合物的某些基团的定义如下(未定义的基团如前任一方案所述)：Ar3a、Ar3b、Ar3c和Ar3d相同。
本发明一优选实施方案中，所述的如式IV所示化合物的某些基团的定义如下(未定义的基团如前任一方案所述)：Ar3a、Ar3b、Ar3c和Ar3d相同，Ar3a、Ar3b、Ar3c和Ar3d为R3a-1取代的C6-C14的芳基。
本发明一优选实施方案中，所述的如式IV或如式IV’所示化合物的某些基团的定义如下(未定义的基团如前任一方案所述)：R7a、R7c、R8a和R8c相同，R7b和R8b相同。
本发明一优选实施方案中，所述的如式IV或如式IV’所示化合物的某些基团的定义如下(未定义的基团如前任一方案所述)：R7a、R7c、R8a和R8c为氢，R7b和R8b相同，R7b和R8b为C1-C4的烷基。
本发明一优选实施方案中，所述的如式IV或如式IV’所示化合物的某些基团的定义如下(未定义的基团如前任一方案所述)：
Ar3a、Ar3b、Ar3c和Ar3d独立地为未取代或R3a-1取代的C6-C14的芳基；每个R3a-1独立地为C1-C4的烷基；
Ar3a、Ar3b、Ar3c和Ar3d相同；
R7a、R7c、R8a和R8c为氢，R7b和R8b独立地为C1-C4的烷基，且R7b和R8b相同；
R5和R6为氢；
为单键或双；
或者，R5和R6和与其相连的碳原子一起形成
本发明一优选实施方案中，所述的如式IV或如式IV’所示化合物的某些基团的定义如下(未定义的基团如前任一方案所述)：
Ar3a、Ar3b、Ar3c和Ar3d独立地为R3a-1取代的C6-C14的芳基；每个R3a-1独立地为C1-C4的烷基；
Ar3a、Ar3b、Ar3c和Ar3d相同；
R7a、R7c、R8a和R8c为氢，R7b和R8b独立地为C1-C4的烷基，且R7b和R8b相同；
R5和R6为氢；
为单键或双键；
或者，R5和R6和与其相连的碳原子一起形成
本发明一优选实施方案中，所述的如式IV或如式IV’所示化合物的某些基团的定义如下(未定义的基团如前任一方案所述)：
Ar3a、Ar3b、Ar3c和Ar3d独立地为R3a-1取代的C6-C14的芳基；每个R3a-1独立地为C1-C4的烷基，优选叔丁基；
Ar3a、Ar3b、Ar3c和Ar3d相同；
R7a、R7c、R8a和R8c为氢，R7b和R8b独立地为C1-C4的烷基，且R7b和R8b相同；
R5和R6为氢；
为单键。
本发明一优选实施方案中，所述的如式IV可为以下任一结构：
本发明一优选实施方案中，所述的如式IV’可为以下任一结构：
本发明还提供了一种所述的化合物IV-1((R,R,R,R)-(DTB-SIPE)Pd(cin)Cl)或化合物IV-3((R,R,R,R)-(SIPE)Pd(cin)Cl)的晶型，在使用辐射源为Ga-Kα的单晶X射线衍射光谱中，
所述的化合物IV-1的单晶属斜方晶系，空间群为P212121，其晶胞参数：
α＝90°，
β＝90°，
γ＝90°，晶胞体积
晶胞内不对称单位数Z＝4，单晶参数可为表1中的参数；
所述的化合物IV-3的单晶属斜方晶系，空间群为P212121，其晶胞参数：
α＝90°，
β＝90°，
γ＝90°，晶胞体积
晶胞内不对称单位数Z＝4，单晶参数可为表2中的参数；
单晶参数：
表1化合物IV-1(R,R,R,R)-(DTB-SIPE)Pd(cin)Cl的单晶数据
表2化合物IV-3(R,R,R,R)-(SIPE)Pd(cin)Cl的单晶数据
本发明还提供了一种所述的化合物IV-1或化合物IV-3的单晶的制备方法，其包括如下步骤：将化合物IV-1或化合物IV-3与氯代烷烃溶剂形成溶液，过滤，将滤液静置于烷烃类溶剂的氛围中得到所述的单晶即可。
所述的将滤液静置于烷烃类溶剂的氛围中的操作优选包括如下步骤：将滤液置于烷烃溶剂的容器内，静置，更优选将滤液置于装有烷烃溶剂的广口瓶中静置。
所述的氯代烷烃溶剂可为本领域的常规氯代烷烃类溶剂，优选氯仿和/或二氯甲烷，例如，氯仿。所述的氯代烷烃类溶剂的用量不作具体限定，只要能够溶解化合物IV-1或化合物IV-3，得到澄清透明的溶液即可。一般地，所述的氯代烷烃类溶剂与化合物IV-1或化合物IV-3的体积质量比为0.1～0.5L/g，例如：0.2L/g。
所述的烷烃类溶剂可为本领域的常规烷烃类溶剂，优选正戊烷和/或正己烷，例如，正己烷。
所述的过滤可为本领域进行此类操作的常规过滤，优选为用滤膜过滤。
所述的单晶的制备方法还可进一步包括如下操作，所述的单晶生成后，在显微镜下挑选。
本发明提供了一种如式IV或如式IV’所示化合物的制备方法，其包括以下步骤：有机溶剂中，在碱的作用下，将如式V或如式V’所示化合物与如式VI所示化合物进行如下所示的反应，即可；
其中，Ar3a、Ar3b、Ar3c、Ar3d、R5、R6、R7a、R7b、R7c、R8a、R8b、R8c和
均同前所述。
所述的如式IV或如式IV’所示化合物的制备方法中，所述的反应的条件和操作可为本领域该类反应常规的条件和操作。
本发明提供了一种化合物1的制备方法，其包括以下步骤：溶剂中，在钯复合物和碱的作用下，将如式II所示化合物和如式III所示化合物进行如下所示的偶联反应，即可；所述的化合物1为如式I所示化合物或如式I’所示化合物；
其中，
X为Cl、Br、I、OTs或OTf；
Y为B(OH)2、
或BF3K；
Ar1和Ar2独立地为C6-C14的芳基、或“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基；
Z1、Z2、Z3、W1、W2和W3独立地为N或CR；
每个R、R1、R2、R3和R4独立地为氢、羟基、醛基、氨基、硝基、氰基、卤素、未取代或R1-1取代的C1-C4的烷基、未取代或R1-2取代的C1-C4的烷氧基、未取代或R1-3取代的C6-C14的芳基、未取代或R1-4取代的“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的C5-C14的杂芳基、
每个R1-1、R1-2、R1-3和R1-4独立地为卤素、C1-C4的烷基、C1-C4的烷氧基、或C6-C14的芳基；
每个R1-5独立地为羟基、C1-C4的烷基或C1-C4的烷氧基；
每个R1-6和R1-7独立地为氢或C1-C4的烷基；
或者，R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成未取代或Ra取代的C6-C14的芳基、或未取代或Rb取代的“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基；
每个Ra和Rb独立地为羟基、醛基、氨基、硝基、氰基、卤素、未取代或Ra-1取代的C1-C4的烷基、未取代或Ra-2取代的C1-C4的烷氧基、
每个Ra-1和Ra-2独立地为卤素、C1-C4的烷基、C1-C4的烷氧基、或C6-C14的芳基；
每个Ra-3独立地为羟基、C1-C4的烷基或C1-C4的烷氧基；
每个Ra-4和Ra-5独立地为氢或C1-C4的烷基；
所述的钯复合物为如式IV或如式IV’所示化合物，
其中，Ar3a、Ar3b、Ar3c、Ar3d、R5、R6、R7a、R7b、R7c、R8a、R8b和R8c均同前所述；
当钯复合物为
时，所述的化合物1为如式I所示化合物；
当钯复合物为
时，所述的化合物1为如式I’所示化合物。
本发明一优选实施方案中，当Ar1为C6-C14的芳基时，所述的C6-C14的芳基为C6-C10的芳基，例如苯基或萘基，优选苯基；
本发明一优选实施方案中，当Ar1为“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基时，所述的5-14元的杂芳基为5-6元的单环杂芳基、或、6-14元的稠杂芳基，优选5-6元的单环杂芳基，所述的5-6元的单环杂芳基可为呋喃基、噻吩基、吡咯基、吡啶基、哒嗪基、嘧啶基或吡嗪基，优选吡啶基。
本发明一优选实施方案中，当Ar2为C6-C14的芳基时，所述的C6-C14的芳基为C6-C10的芳基，例如苯基或萘基，优选苯基；
本发明一优选实施方案中，当Ar2为“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基时，所述的5-14元的杂芳基为5-6元的单环杂芳基、或、6-14元的稠杂芳基，优选5-6元的单环杂芳基，所述的5-6元的单环杂芳基可为呋喃基、噻吩基、吡咯基、吡啶基、哒嗪基、嘧啶基或吡嗪基，优选吡啶基。
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为卤素时，所述的卤素独立地为F、Cl、Br或I，优选F。
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为R1-1取代的C1-C4的烷基时，所述的R1-1可独立地为一个或多个，例如1、2或3个，当存在多个R1-1时，所述的R1-1可相同或不同。
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为未取代或R1-1取代的C1-C4的烷基时，所述的C1-C4的烷基可独立地为甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基，优选甲基。
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为R1-2取代的C1-C4的烷氧基时，所述的R1-2可独立地为一个或多个，例如1、2或3个，当存在多个R1-2时，所述的R1-2可相同或不同。
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为未取代或R1-2取代的C1-C4的烷氧基时，所述的C1-C4的烷氧基可独立地为甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基或叔丁氧基，优选甲氧基或乙氧基。
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为R1-3取代的C6-C14的芳基时，所述的R1-3可独立地为一个或多个，例如1、2、3或4个，当存在多个R1-3时，所述的R1-3可相同或不同。
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为未取代或R1-3取代的C6-C14的芳基时，所述的C6-C14的芳基可独立地为C6-C10的芳基，优选苯基或萘基。
本发明一优选实施方案中，当R1-1、R1-2、R1-3和R1-4独立地为卤素时，所述的卤素独立地为F、Cl、Br或I，优选F。
本发明一优选实施方案中，当R1-1、R1-2、R1-3、R1-4、R1-5、R1-6和R1-7独立地为C1-C4的烷基时，所述的C1-C4的烷基可独立地为甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基，优选甲基。
本发明一优选实施方案中，当R1-1、R1-2、R1-3、R1-4和R1-5独立地为C1-C4的烷氧基时，所述的C1-C4的烷氧基可独立地为甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基或叔丁氧基，优选甲氧基或乙氧基。
本发明一优选实施方案中，当R1-1、R1-2、R1-3、R1-4独立地为C6-C14的芳基时，所述的C6-C14的芳基可独立地为C6-C10的芳基，优选苯基。
本发明一优选实施方案中，当R1-5、R1-6和R1-7独立地为C1-C4的烷基时，所述的C1-C4的烷基独立地为甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基，优选甲基或乙基。
本发明一优选实施方案中，当R1-5为C1-C4的烷氧基时，所述的C1-C4的烷氧基为甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基或叔丁氧基，优选甲氧基或乙氧基。
本发明一优选实施方案中，当R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成Ra取代的C6-C14的芳基时，所述的Ra可独立地为一个或多个，例如1、2或3个，当存在多个Ra时，所述的Ra可相同或不同。
本发明一优选实施方案中，当R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成未取代或Ra取代的C6-C14的芳基时，所述的C6-C14的芳基为C6-C10的芳基，优选苯基或萘基。
本发明一优选实施方案中，当R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成Rb取代的“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基时，所述的Rb可独立地为一个或多个，例如1、2或3个，当存在多个Rb时，所述的Rb可相同或不同。
本发明一优选实施方案中，当R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成未取代或Rb取代的“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基时，所述的5-14元的杂芳基可为5-6元的单环杂芳基或6-14元的稠杂芳基，优选5-6元的单环杂芳基。所述的5-6元的单环杂芳基可为呋喃基、噻吩基、吡咯基、吡啶基、嘧啶基、哒嗪基或吡嗪基，优选噻吩基、吡咯基、吡啶基或嘧啶基，例如
所述的6-14元的稠杂芳基可为6-10元的稠杂芳基，例如吲哚基、异吲哚基、喹啉基、异喹啉基，优选吲哚基，例如
本发明一优选实施方案中，当Ra和Rb独立地为卤素时，所述的卤素独立地为F、Cl、Br或I。
本发明一优选实施方案中，当Ra和Rb独立地为Ra-1取代的C1-C4的烷基时，所述的Ra-1可独立地为一个或多个，例如1、2或3个，当存在多个Ra-1时，所述的Ra-1可相同或不同。
本发明一优选实施方案中，当Ra和Rb独立地为未取代或Ra-1取代的C1-C4的烷基时，所述的C1-C4的烷基可独立地为甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基。
本发明一优选实施方案中，当Ra和Rb独立地为Ra-2取代的C1-C4的烷氧基时，所述的Ra-2可独立地为一个或多个，例如1、2或3个，当存在多个Ra-2时，所述的Ra-2可相同或不同。
本发明一优选实施方案中，当Ra和Rb独立地为未取代或Ra-2取代的C1-C4的烷氧基时，所述的C1-C4的烷氧基可独立地为甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基或叔丁氧基。
本发明一优选实施方案中，当Ra-1和Ra-2独立地为卤素时，所述的卤素独立地为F、Cl、Br或I。
本发明一优选实施方案中，当Ra-1、Ra-2、Ra-3、Ra-4和Ra-5独立地为C1-C4的烷基时，所述的C1-C4的烷基可独立地为甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基，优选甲基或乙基。
本发明一优选实施方案中，当Ra-1、Ra-2和Ra-3独立地为C1-C4的烷氧基时，所述的C1-C4的烷氧基可独立地为甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基或叔丁氧基，优选甲氧基。
本发明一优选实施方案中，当Ra-1和Ra-2独立地为C6-C14的芳基时，所述的C6-C14的芳基可为C6-C10的芳基，例如苯基。
本发明一优选实施方案中，当Ra-3、Ra-4和Ra-5独立地为C1-C4的烷基时，所述的C1-C4的烷基可独立地为甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基。
本发明一优选实施方案中，当Ra-3为C1-C4的烷氧基时，所述的C1-C4的烷氧基可独立地为甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基或叔丁氧基。
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为R1-1取代的C1-C4的烷基时，所述的R1-1取代的C1-C4的烷基独立地优选-CF3。
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为R1-2取代的C1-C4的烷氧基时，所述的R1-2取代的C1-C4的烷氧基独立地优选-OBn或
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为R1-3取代的C6-C14的芳基时，所述的R1-3取代的C6-C14的芳基独立地优选
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为
时，所述的
独立地优选
本发明一优选实施方案中，当R、R1、R2、R3和R4独立地为
时，所述的
独立地优选
本发明一优选实施方案中，当Ra和Rb独立地为
所述的
优选
本发明一优选实施方案中，当Ra和Rb独立地为
时，所述的
优选
本发明一优选实施方案中，所述的如式I或式I’所示化合物的某些基团的定义如下(未定义的基团如前任一方案所述)：
X为Cl、Br或OTf；
Y为B(OH)2、BPin、Bneo或BF3K；
Ar1和Ar2独立地为C6-C14的芳基；
Z1、Z2、Z3、W1、W2和W3独立地为N或CR；
每个R、R1、R2、R3和R4独立地为氢、羟基、醛基、氨基、硝基、氰基、卤素、未取代或R1-1取代的C1-C4的烷基、未取代或R1-2取代的C1-C4的烷氧基、或未取代或R1-3取代的C6-C14的芳基；
每个R1-1、R1-2、R1-3和R1-4独立地为卤素、C1-C4的烷基、或C1-C4的烷氧基；
每个R1-5独立地为C1-C4的烷基或C1-C4的烷氧基；
每个R1-6和R1-7独立地为氢或C1-C4的烷基；
或者，R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成未取代或Ra取代的C6-C14的芳基、或未取代或Rb取代的“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基；
每个Ra和Rb独立地为羟基、醛基、氨基、硝基、氰基、卤素、未取代的C1-C4的烷基、未取代的C1-C4的烷氧基、或
每个Ra-3独立地为C1-C4的烷基或C1-C4的烷氧基。
本发明一优选实施方案中，所述的如式I或式I’所示化合物可为以下任一结构：
所述的偶联反应中，所述的溶剂可为有机溶剂、或有机溶剂和水的混合溶剂。所述的有机溶剂优选醇类溶剂、芳烃类溶剂和醚类溶剂中的一种或多种，更优选醇类溶剂和/或芳烃类溶剂。所述的醇类溶剂优选乙醇、异丙醇和叔丁醇中的一种或多种，更优选叔丁醇。所述的芳烃类溶剂优选甲苯。所述的醚类溶剂优选四氢呋喃(THF)。当所述的溶剂为有机溶剂和水的混合溶剂时，所述的有机溶剂和水的体积比优选5:1-10:1，更优选8:1-10:1，例如9:1。
所述的偶联反应中，所述的碱优选碱金属氢氧化物、碱金属碳酸盐、碱金属磷酸盐和碱金属醇盐中的一种或多种，更优选碱金属氢氧化物。所述的碱金属氢氧化物优选氢氧化钾。所述的碱金属碳酸盐优选碳酸钾和/或碳酸铯。所述的碱金属磷酸盐优选磷酸钾。所述的碱金属醇盐优选甲醇钾和/或叔丁醇钾，更优选叔丁醇钾。
所述的偶联反应中，所述的如式III所示化合物与所述的如式II所示化合物的摩尔比优选1:1-5:1，更优选1:1-2:1，例如1.2:1、1.3:1或2:1。
所述的偶联反应中，所述的碱与所述的如式II所示化合物的摩尔比优选1:1-:1，更优选1:1-3:1，例如1.3:1、2:1或2.5:1。
所述的偶联反应中，所述的如式II所示化合物在所述的溶剂中的摩尔浓度优选0.1-0.5mol/L，更优选0.1-0.3mol/L，例如0.2mol/L或0.25mol/L。
所述的偶联反应中，所述的钯复合物与所述的如式II所示化合物的摩尔比优选1:10-1:500，更优选1:50-1:200，例如1:50、1:100或1:200。
所述的偶联反应中，所述的偶联反应温度优选30-60℃。例如30℃、50℃或60℃。
所述的偶联反应中，所述的偶联反应的反应进程可通过本领域常规的手段进行监控(例如TLC、HPLC或LC-MS)，所述的偶联反应的时间优选24-48h。
所述的偶联反应优选在保护气体氛围下进行，所述的保护气体可为本领域常规的保护气体，例如氮气。
所述的偶联反应中，较佳地，所述的反应结束后，其还可进一步包括后处理操作，所述的后处理可包括以下步骤：将反应液经分离纯化，即可。所述的分离纯化优选柱层析分离。
本发明中，术语卤素表示氟、氯、溴、或碘。
本发明中，术语烷基为具有指定碳原子数目的支链或直链的饱和脂肪族烃基；例如，所述的C1-C4烷基为甲基、乙基、正丙基、异丙基、正丁基、叔丁基或异丁基。
本发明中，术语烷氧基表示烷基与氧原子连接后的生成基团，即“
”，R为烷基。C1-C4的烷氧基是指甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基或叔丁氧基。
本发明中，术语“芳基”是指具有指定的碳原子数的芳香基团，优选单环、双环或者三环的芳香基团，当为双环或者三环时，每个环均满足休克尔规则。本发明的C6-10的芳基指含有6～10个碳原子的芳香基团，例如苯基或萘基。
本发明中，术语杂芳基表示各环中可高达14个原子的稳定单环、二环或三环，其中至少一个环是芳香环并且含有1-4个选自O、N和S的杂原子。在此定义范围内的杂环芳基包括5-6元的单环杂芳基、6-14元的稠杂芳基。5-6元的单环杂芳基包括但不限于：呋喃基、噻吩基、吡唑基、吡咯基、哒嗪基、吡啶基、嘧啶基、噁唑基、异噁唑基等。6-14元的稠杂芳基包括将单环的杂芳基稠合在芳基、杂芳基、环烷基或杂环烷基上，实例包括但不限于吖啶基、咔唑基、噌啉基、喹喔啉基、吲哚基、异吲哚基、苯并吡唑基、苯并噻吩基、苯并呋喃基、喹啉基、异喹啉基、吡咯并吡啶基吡嗪基、四氢喹啉或
在符合本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于：
(1)本发明的制备方法制得的轴手性联芳香化合物的收率高，反应立体选择性强，ee值可高达85％以上，绝大部分在90％以上。
(2)本发明的制备方法底物适用性广，对杂环底物有很好的适用性，合成的轴手性联芳香化合物具有多种结构。
(3)本发明的钯复合物结构新颖，适用于偶联反应，合成的轴手性联芳香化合物结构多样，收率高，立体选择性好。
附图说明
图1为化合物IV-1的单晶图。
图2为化合物IV-3的单晶图。
图3为化合物I-4的单晶图。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
化合物A系列化合物的制备
实施例1：1,3-二(2,6-二((R)-1-(3,5-二叔丁基苯基)乙基)-4-甲基苯基)-4,5-二氢-1H-咪唑盐(化合物V-1)
步骤1：(Z)-N,N’-二(4-甲氧基-2,6-二((S)-1-苯乙基)苯基)乙烯-1,2-二胺2-(1-(3,5-二叔丁基苯基)乙烯基)-4,4,5,5-四甲基-1,3,2-二氧硼戊环(中间体2)的合成
向500mL圆底烧瓶加入1,3-双(二苯基膦丙烷)二氯化镍(2.48g，4.6mmol)，四氢呋喃100mL，二异丁基氢化铝(122mL，183.1mmol)，将反应也冷却至0℃，中间体1溶于100mL四氢呋喃中，缓慢滴加至反应液中，滴加完毕，将反应液转移至室温搅拌2h，再将反应也冷却至0℃，缓慢滴加2-甲氧基-4,4,5,5-四甲基-1,3,2-二氧硼戊环(30mL，228.9mmol)，将反应液转移至80℃油浴锅内加热搅拌24h。停止反应，将反应液转移至0℃冷阱中，缓慢滴加水淬灭反应，减压去除部分四氢呋喃溶液，加入适量乙二胺四乙酸水溶液以及乙酸乙酯溶液，搅拌3h，乙酸乙酯萃取，有机相经无水硫酸钠干燥后，浓缩，经柱色谱纯化，得油状物中间体2(44.5g，收率＝85％)。
步骤2：2,6-二(1-(3,5-二叔丁基苯基)乙烯基)-4-甲基苯胺(中间体4)的合成
向100mL耐压瓶中加入2,6-二溴-4-甲基苯胺(43.9g,128.3mmol)，[1,3-双(2,6-二异丙基苯)咪唑-2-叉](3-氯吡啶)二氯化钯(729mg,1.2mmol)，氢氧化钾(9.8g,174.9mmol)，中间体2(15.4g,58.3mol)，100mL四氢呋喃溶液，于100℃条件下加热12h。停止反应，过短硅胶柱，乙酸乙酯冲洗，减压浓缩，经柱色谱纯化，得浅色固体中间体4(27g，收率＝87％)
步骤3：2,6-二((R)-1-(3,5-二叔丁基苯基)乙基)-4-甲基苯胺(中间体5)的合成
向300mL反应瓶加入中间体4(18.5g,34.5mmol),120mL MeOH，另取干燥小瓶加入双(降冰片二烯)四氟硼酸铑((NBD)2RhBF4，0.3mol％)，(Rc,Sp)-DuanPhos(0.36mol％)，DCM(12mL)搅拌15min后加入300mL反应瓶中，混合物于30℃下通入80atm H2，反应48个小时后，停止反应。减压去除甲醇，过短硅胶柱，乙酸乙酯冲洗，浓缩后经柱色谱纯化，得油状物中间体5(13.0g，收率＝70％)。1H NMR(400MHz,CDCl3)δ:7.22(t,J＝1.8Hz,2H),7.02(d,J＝1.9Hz,4H),6.97(s,2H),4.02(q,J＝7.1Hz,2H),3.29(s,2H),2.33(s,3H),1.59(d,J＝7.2Hz,6H),1.25(s,36H)。13C NMR(101MHz,Chloroform-d)δ150.7,144.8,139.6,130.6,126.8,126.2,121.8,120.1,41.1,34.9,31.6,24.9,22.2,21.3.
步骤4：N,N-二(2,6-二((R)-1-(3,5-二叔丁基苯基)乙基)-4-甲基苯基)草酰胺(化合物6)的合成
向50mL圆底瓶内中间体5(1.89g,3.5mol)，四氢呋喃15mL，三乙胺(535μL,3.9mol)，将反应液降温至0℃，缓慢滴加草酰氯(163μL,1.9mol)，将反应液升至室温，继续搅拌过夜。停止反应，向反应液内加入适量饱和碳酸氢钠水溶液淬灭反应，二氯甲烷萃取，有机相经无水硫酸钠干燥后浓缩，经柱色谱纯化，分离得白色泡沫状中间体6(1.68g,收率＝85％)。1H NMR(400MHz,CDCl3)δ:8.58(s,2H),7.25–7.20(m,4H),7.08(d,J＝1.8Hz,8H),6.93(s,4H),4.23(q,J＝7.0Hz,4H),2.27(s,6H),1.54(d,J＝7.1Hz,6H),1.26(s,72H),0.93(d,J＝6.6Hz,6H).13C NMR(101MHz,CDCl3)δ:201.6,159.2,150.4,144.3,137.7,128.4,126.4,122.1,120.0,40.3,34.8,31.5,31.4,3.,24.9,22.2,21.7.
HRMS(ESI)计算值(C80H116N3O2[M+H]+)1150.9062,实测值1150.9054.
步骤5：N,N-二(2,6-二((R)-1-(3,5-二叔丁基苯基)乙基)-4-甲基苯基)乙烷-1,2-二胺(中间体7)的合成
向100mL圆底瓶内中间体6(3g,2.65mol)，四氢呋喃30mL，将反应液降温至0℃，分批加入四氢铝锂(540.0mg,13.5mol)，将反应液升温至回流，继续搅拌24h。停止反应，向反应液内加入15％氢氧化钾水溶液(0.5mL)淬灭反应，室温搅拌15min，加入适量硫酸镁抽滤，乙酸乙酯冲洗，有机相经无水硫酸钠干燥后浓缩；将上述干燥后混合物溶于30mL甲苯溶液，向其中滴加BH3-Me2S(5.4mL.2.0M in THF,10.8mmol)，回流搅拌12h。停止反应，向反应液内缓慢加入1M盐酸(20mL)，搅拌3h，二氯甲烷萃取，有机相再经氢氧化钠水溶液调碱性后干燥浓缩，得白色固体中间体7(1.8g,收率＝62％)。1H NMR(400MHz,CDCl3)δ:7.22(t,J＝1.8Hz,4H),7.12(d,J＝1.9Hz,8H),7.01(s,4H),4.62(q,J＝7.1Hz,4H),3.12(d,J＝7.2Hz,2H),2.60(d,J＝7.5Hz,2H),2.35(s,6H),1.65(d,J＝7.1Hz,12H),1.25(s,72H)..13C NMR(101MHz,CDCl3)δ:150.3,145.6,142.5,140.9,132.4,126.4,121.9,119.6,77.4,77.1,76.7,53.4,51.9,39.7,34.8,31.5,23.4,21.5.
HRMS(ESI)计算值(C80H117N2[M+H]+)1105.9211,实测值1105.9201.
步骤6：1,3-二(2,6-二((R)-1-(3,5-二叔丁基苯基)乙基)-4-甲基苯基)-4,5-二氢-1H-咪唑盐(化合物V-1)的合成
向50mL茄形瓶中加入化合物7(1.5g,2.35mmol)，NH4Cl(108.6mg，2.03mmol)，4.7mL原甲酸三乙酯，经氮气置换后，混合物于115℃下反应20小时，过短硅胶柱，浓缩后经柱色谱纯化，分离得白色化合物V-1(1.4g，收率＝90％)。1H NMR(400MHz,CDCl3)δ:8.24(s,1H),7.29(d,J＝2.2Hz,4H),7.04(s,4H),6.92(t,J＝1.9Hz,8H),4.49–4.32(m,4H),4.20(d,J＝11.4Hz,2H),3.89(q,J＝7.0Hz,2H),2.31(s,6H),1.84(d,J＝7.0Hz,6H),1.30(s,36H),1.19(s,36H),1.06(d,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ:158.5,151.3,151.0,144.0,143.6,143.4,143.1,141.5,128.6,128.3,128.0,121.6,121.1,120.9,120.8,77.4,77.0,76.7,54.1,40.4,38.7,34.9,34.9,31.5,31.5,23.2,22.9,21.7。
HRMS(ESI)计算值(C81H115N2[M+H]+)1115.9055,实测值1115.9038.
参照是实施例1的方法，采用不同的原料，合成了化合物V-2～V-7：
实施例2：钯复合物的合成
通用方法A
其中，Ar3a、Ar3b、Ar3c、Ar3d、R5、R6、R7a、R7b、R7c、R8a、R8b和R8c均同前所述。
在手套箱内，向8mL小瓶内依次加入化合物V(0.3mmol)，叔丁醇钾(30.3mg,0.27mmol)，四氢呋喃(1.2mL,0.25M)，于室温下搅拌4h。然后将[Pd(η3-cin)(μ-Cl)]2(77.7mg,0.15mmol)加入，继续室温搅拌12h。停止反应，将反应液过短硅胶柱，用乙酸乙酯冲洗，有机相浓缩后经柱色谱纯化，得淡黄色固体。
实施例3：钯复合物(R,R,R,R)-(DTB-SIPE)Pd(cin)Cl(化合物IV-1)的合成
按照通用方法A，向8mL小瓶内加入化合物V-1(345.2mg,0.3mmol)，分离得淡黄色固体279.8mg(收率:68％，化合物IV-1)。1H NMR(400MHz,CDCl3)δ:7.49(s,4H),7.33–7.28(m,3H),7.22(m,1H),7.17(m,2H),7.09(m,3H),7.07–6.95(m,8H),5.07(s,1H),4.73(d,J＝7.8Hz,2H),4.20(m,1H),3.33(m,2H),2.80(m,2H),2.41(s,6H),1.72(m,12H),1.38(s,2H),1.35–1.26(s,36H),1.21(s,36H),1.18(s,2H).13C NMR(101MHz,CDCl3)δ:150.8,150.2,147.3,144.3,143.5,143.1,138.3,136.9,135.8,128.8,128.2,127.8,127.1,126.3,123.2,121.5,120.0,119.5,111.3,92.6,52.7,44.9,40.95,39.6,35.0,34.8,31.7,31.5,26.3,25.2,21.8.
HRMS(MALDI)计算值(C90H123N2Pd[M-Cl]+)1337.8743,实测值1337.8721
实施例4：钯复合物(R,R,R,R)-(DM-SIPE)Pd(cin)Cl(化合物IV-2)的合成
按照通用方法A，向8mL小瓶内加入化合物V-2(55.2mg,0.06mmol)，分离得黄色泡沫状固体37.1mg(收率:60％，化合物IV-2)。1H NMR(400MHz,CDCl3)δ:7.39–7.23(m,6H),7.21–7.00(m,7H),6.87(m,5H),6.77(m,3H),4.73(m,4H),4.00–3.66(m,1H),3.21(m,2H),2.53(s,2H),2.44(s,6H),2.35(s,6H),2.22(s,12H),2.12(s,1H),1.76(d,J＝7.1Hz,6H),1.64(d,J＝7.0Hz,6H).13C NMR(101MHz,CDCl3)δ:208.9,148.2,144.9,142.8,138.2,137.6,136.2,128.6,128.2,128.0,127.9,127.8,127.4,126.7,126.6,125.0,110.5,93.5,53.4,45.3,41.2,38.5,25.9,25.5,22.1,21.8,21.7,21.6,21.5,14.3.
HRMS(MALDI)计算值(C66H75N2Pd[M-Cl]+)997.4981,实测值997.4924.
实施例5：钯复合物(R,R,R,R)-(SIPE)Pd(cin)Cl(化合物IV-3)的合成
按照通用方法A，向8mL小瓶内加入化合物V-3(420.0mg,0.6mmol)，分离得浅色固体430.2mg(收率:77％，化合物IV-3)。1H NMR(400MHz,CDCl3)δ:7.67(m,4H),7.39(t,J＝7.6Hz,2H),7.28(m,7H),7.24–7.09(m,14H),6.88(d,J＝11.4Hz,2H),4.94–4.45(m,5H),4.29(m,1H),3.22(m,2H),2.46(m,2H),2.38(m,6H),1.77(m,6H),1.62(s,6H).13C NMR(101MHz,CDCl3)δ:147.9,147.9,145.0,142.3,137.9,136.1,128.9,128.7,128.5,128.3,128.1,127.5,127.4,127.1,126.2,126.1,109.8,109.1,95.2,92.2,77.3,53.3,44.1,41.2,41.0,38.2,25.0,24.2,24.0,21.8.
HRMS(ESI)计算值(C58H59N2Pd[M-Cl]+)885.3729,实测值885.3695.
实施例6：钯复合物(R,R,R,R)-(DTB-SIPE)Pd(cin)Cl(化合物IV-4)的合成
按照通用方法A，向8mL小瓶内加入化合物V-4(127.0mg,0.1mmol)，分离得黄色固体430.2mg(收率:77％，化合物IV-4)。1H NMR(400MHz,CDCl3)δ:7.62(s,2H),7.57(s,3H),7.38(s,2H),7.34–7.25(m,3H),7.22(m,4H),7.02(s,2H),6.80–6.69(m,7H),6.03(d,J＝6.9Hz,2H),5.21(s,2H),4.84(s,1H),4.52(d,J＝12.8Hz,1H),4.21–4.11(m,2H),2.56(s,6H),2.08(s,1H),1.64(m,12H),1.40(s,36H),0.89(s,36H).13C NMR(101MHz,CDCl3)δ:150.4,145.0,145.0,144.2,143.5,142.8,140.5,138.4,138.2,133.9,128.9,128.6,128.1,127.4,126.7,126.6,126.2,125.6,123.5,121.0,120.6,120.2,119.5,41.7,40.1,35.2,34.4,31.8,31.8,31.3,27.7,24.5,22.2.
HRMS(ESI)计算值(C100H125N2Pd[M-Cl]+)1455.8893,实测值1456.8885.
实施例7：钯复合物(R,R,R,R)-(DM-ANIPE)Pd(cin)Cl(化合物IV-5)的合成
按照通用方法A，向8mL小瓶内加入化合物V-5(102.0mg，0.11mmol)，分离得黄色固体95.1mg(收率:75％，化合物IV-5)。1H NMR(400MHz,CDCl3)δ:7.48(s,2H),7.33(d,J＝8.2Hz,4H),7.27–7.13(m,10H),7.00(s,1H),6.94–6.80(m,4H),6.28(s,4H),5.94(d,J＝6.9Hz,2H),5.77(s,2H),4.80(m,2H),4.56(m,1H),4.19(m,2H),2.51(m,6H),2.35(d,J＝3.6Hz,12H),2.19(s,3H),1.56(d,J＝7.3Hz,12H),1.39(s,12H).13C NMR(101MHz,CDCl3)δ:188.6,145.1,144.7,143.2,140.5,139.2,137.9,137.5,137.0,133.9,129.1,128.3,128.3,128.2,128.0,127.8,127.2,126.7,126.7,126.1,125.7,125.5,125.4,125.3,120.1,109.7,93.9,44.4,41.6,38.7,29.8,25.3,24.2,22.3,21.8,21.6,21.6,20.4.
HRMS(MALDI)计算值(C76H77N2Pd[M-Cl]+)1124.5164,实测值1124.5275.
实施例8：钯复合物(R,R,R,R)-(ANIPE)Pd(cin)Cl(化合物IV-6)的合成
按照通用方法A，向8mL小瓶内加入化合物V-6(100.0mg,0.12mmol)，分离得黄色固体89.2mg(收率:71％，化合物IV-6)。1H NMR(400MHz,CDCl3)δ:7.77(d,J＝7.7Hz,2H),7.64(d,J＝7.4Hz,2H),7.58–7.40(m,7H),7.35(m,8H),7.00(s,1H),6.93(s,1H),6.86(t,J＝7.6Hz,2H),6.75–6.66(m,4H),6.30(m,6H),5.99(m,2H),5.05(m,2H),4.92–4.40(m,2H),4.39–4.23(m,2H),2.53(m,6H),1.59(m,12H),1.46(m,2H).13C NMR(101MHz,CDCl3)δ:188.3,145.1,144.8,144.5,142.8,140.7,139.52,137.5,134.0,129.1,129.0,128.7,128.3,128.2,128.2,128.0,127.7,127.5,127.2,126.9,126.9,126.5,126.3,126.1,125.4,125.3,120.7,109.1,95.3,91.0,47.2,44.2,41.8,41.6,38.8,25.4,22.8,22.7,22.2.
HRMS(ESI)计算值(C68H61N2Pd[M-Cl]+)1007.3885,实测值1007.3842.
实施例9：钯复合物(R,R,R,R)-(IPE)Pd(cin)Cl(化合物IV-7)的合成
按照通用方法A，向8mL小瓶内加入化合物V-7(100.0mg,0.12mmol)，分离得黄色固体89.2mg(收率:71％，化合物IV-7)。1H NMR(400MHz,CDCl3)δ:7.80(d,J＝7.6Hz,2H),7.66(d,J＝7.4Hz,2H),7.56–7.30(m,13H),7.23(m,4H),7.20–7.13(m,2H),7.08–6.98(m,4H),6.85(m,2H),5.90(s,2H),5.04(m,1H),4.84(q,J＝7.3Hz,1H),4.74–4.46(m,2H),4.17(m,2H),2.58(t,J＝7.8Hz,1H),2.45(m,6H),1.70–1.54(m,12H),1.29(m,1H).13C NMR(101MHz,CDCl3)δ:181.9,181.3,147.5,144.9,144.8,144.5,144.4,141.3,139.0,138.0,137.5,135.3,129.0,128.6,128.5,128.4,128.2,128.1,128.0,128.0,127.6,127.5,127.2,127.0,126.9,126.8,126.3,126.3,126.0,124.6,124.5,109.1,108.8,93.6,90.1,46.9,44.4,41.2,41.1,38.6,24.6,22.4,22.0,22.0.
HRMS(ESI)计算值(C58H57N2Pd[M-Cl]+)883.3572,实测值883.3539.
实施例10：化合物IV-1和IV-3的单晶衍射实验
1.单晶培养：将化合物IV-1(30mg)或IV-3(20mg)溶于氯仿(3mL)中，滤膜过滤，将滤液分别置于装有正己烷(15mL)的广口瓶中静置，得到所述的单晶即可。
2.测试参数如上表1和表2所示。
3.测试结果：化合物IV-1和化合物IV-3的构型由单晶衍射确定。
实施例11：反应条件优化
反应以0.1mmol规模进行；收率通过NMR分析测定，以1,3,5-三甲基苯作为内标；ee值通过手性固定相的手性HPLC测定。
实施例12：轴手性联芳香化合物合成
通用方法A:向装有搅拌子的15mL史莱克瓶内依次加入化合物IV-1(2.8mg,2μmol)，氢氧化钾(22.4mg,0.40mmol)，芳基溴代物II(0.2mmol)，芳基硼酸III(0.24mmol)和叔丁醇(1.0mL,0.2M)。置换成氮气氛围后，将反应液于50℃搅拌24h。停止反应，将反应液过短硅胶柱，乙酸乙酯稀释，有机相浓缩后经柱色谱纯化，得到目标产物，ee值经由手性HPLC测得，化合物的构型通过单晶衍射实验测得。
实施例13
通用方法B:向装有搅拌子的15mL史莱克瓶内依次加入化合物IV-1(2.8mg,4μmol)，碳酸铯(162.9mg,0.50mmol)，芳基溴代物II(0.2mmol)，芳基硼酸III(0.40mmol)和叔丁醇/水(9:1,1.0mL,0.2M)。置换成氮气氛围后，将反应液于60℃搅拌24h。停止反应，将反应液过短硅胶柱，乙酸乙酯稀释，有机相浓缩后经柱色谱纯化，得到目标产物，ee值经由手性HPLC测得，化合物的构型通过单晶衍射实验测得。
实施例14
通用方法C:向装有搅拌子的15mL史莱克瓶内依次加入化合物IV-1(1.4mg,1μmol)，叔丁醇钾(29.2mg,0.26mmol)，芳基溴代物II(0.2mmol)，芳基硼酸III(0.26mmol)和甲苯/水(9:1,0.8mL,0.25M)。置换成氮气氛围后，将反应液于30℃搅拌24h。停止反应，将反应液过短硅胶柱，乙酸乙酯稀释，有机相浓缩后经柱色谱纯化，得到目标产物，ee值经由手性HPLC测得，化合物的构型通过单晶衍射实验测得。
实施例15
化合物I-1:按通用方法A制备得白色固体，产率为91％。1H NMR(400MHz,CDCl3)δ:8.03–7.88(m,3H),7.83(d,J＝8.2Hz,1H),7.58(m,1H),7.47–7.35(m,3H),7.34–7.20(m,3H),7.20–7.11(m,2H),3.70(s,3H).13C NMR(101MHz,CDCl3)δ:154.7,134.7,134.4,133.8,133.0,129.6,129.1,128.6,128.3,127.9,127.9,126.5,126.3,126.0,125.8,125.7,125.6,123.7,123.3,113.9,56.8.
HPLC分析(AD-H,1％IPA的环己烷溶液,1mL/min,230nm)测得97％ee:tR(major)＝5.9min,tR(minor)＝7.0min.
化合物I-2:按通用方法A制备得白色固体，产率为98％。1H NMR(400MHz,CDCl3)δ:7.91(d,J＝8.2Hz,2H),7.84(m,2H),7.56(m,1H),7.47–7.39(m,2H),7.38–7.31(m,2H),7.22(d,J＝4.0Hz,2H),7.19–7.11(m,2H),2.09(s,3H).13C NMR(101MHz,CDCl3)δ:137.6,136.2,134.5,133.8,133.6,132.7,132.1,128.7,128.4,127.9,127.7,127.7,126.4,126.3,126.1,126.1,126.0,126.0,125.8,124.9,20.7.
HPLC分析(OJ-H,1％IPA的环己烷溶液,1.0mL/min,254nm)测得95％ee:tR(mior)＝6.8min,tR(major)＝9.3min.
化合物I-3:按通用方法A制备得无色油状物，产率为92％。1H NMR(400MHz,CDCl3)δ:8.14–7.95(m,3H),7.93(d,J＝8.2Hz,1H),7.69(t,J＝7.6Hz,1H),7.60–7.44(m,4H),7.44–7.27(m,4H),7.25–7.17(m,3H),7.03(m,2H),5.11(q,J＝12.6Hz,2H).13C NMR(101MHz,CDCl3)δ:153.7,137.3,134.6,134.4,133.8,133.1,129.5,129.4,128.6,128.6,128.3,127.9,127.9,127.6,126.9,126.5,126.4,126.0,125.8,125.8,125.7,124.7,124.0,116.1,71.4.
HPLC分析(AD-H，1％IPA的环己烷溶液,1.0mL/min,254nm)测得90％ee:tR(major)＝6.1min,tR(minor)＝9.4min.HRMS(ESI)计算值C27H24NO[M+H]+m/z 378.1852,实测值378.1856.
化合物I-4:按通用方法C制备得白色固体，产率为85％。1H NMR(400MHz,CDCl3)δ:7.92(m,3H),7.85(d,J＝8.2Hz,1H),7.63–7.54(m,2H),7.43(m,2H),7.38–7.29(m,2H),7.28–7.14(m,3H),5.06(s,2H),3.44–3.25(m,2H),1.00(t,J＝7.1Hz,3H).13C NMR(101MHz,CDCl3)δ:152.4,134.7,134.4,133.7,133.1,129.8,129.5,128.5,128.3,127.9,127.8,126.2,126.4,126.0,125.8,125.6,125.0,124.14117.2,93.9,64.2,15.1.
HPLC分析(AD-H,1％IPA的环己烷溶液,1.0mL/min,220nm)测得92％ee:tR(major)＝7.8min,tR(minor)＝9.9min.HRMS(ESI)计算值C23H24NO2[M+H]+m/z346.1802,实测值346.1798.
化合物I-4的单晶衍射实验
1.单晶培养：将上述实施例中分离得到的tR(major)＝7.8min处的化合物I-4(20mg)溶于氯仿(1mL)中，滤膜过滤，将滤液置于核磁管中静置，溶剂缓慢挥发后得到所述的单晶即可。
2.测试参数如下表3所示：
表3化合物I-4的单晶数据
3.测试结果：化合物I-4的构型由单晶衍射确定，由此也可以化合物I-1～I-3、I-5～I-40的构型。
化合物I-6:按通用方法C制备得无色油状物，产率为85％。1H NMR(400MHz,CDCl3)δ:7.97(dd,J＝12.4,8.3Hz,2H),7.81(d,J＝8.8Hz,1H),7.75(d,J＝8.8Hz,1H),7.66–7.57(m,1H),7.57–7.46(m,2H),7.42(d,J＝8.4Hz,1H),7.39–7.32(m,1H),7.18(d,J＝8.8Hz,1H),6.95–6.82(m,1H),6.35(d,J＝2.5Hz,1H),4.96(s,1H),4.88(s,1H).13C NMR(101MHz,CDCl3)δ:154.3,151.7,135.4,134.3,132.8,131.6,130.1,129.8,129.3,128.6,127.0,126.7,126.2,125.9,124.5,117.6,115.1,115.1,115.1,107.4,107.3.
HPLC分析(OD-H,15％IPA的环己烷溶液,1.0mL/min,220nm)测得99％ee:tR(minor)＝9.7min,tR(major)＝12.4min HRMS(ESI)计算值C20H15O2[M+H]+m/z287.1067,实测值287.1069.
化合物I-7:按通用方法C制备得无色油状物，产率为96％。1H NMR(400MHz,CDCl3)δ:7.72(m,2H),7.45–7.30(m,3H),7.25(m,1H),7.11(d,J＝8.8Hz,1H),6.91(m,1H),6.47(d,J＝2.5Hz,1H),5.19(s,1H),5.04(s,1H),2.03(s,3H).13C NMR(101MHz,CDCl3)δ:154.3,150.7,139.1,134.6,133.3,131.7,131.1,130.2,129.4,129.0,127.0,124.5,119.1,115.0,106.8,19.6.
HPLC分析(AD-H,10％IPA的环己烷溶液,1.0mL/min,254nm)测得92％ee:tR(minor)＝15.9min,tR(minor)＝21.0min HRMS(ESI)计算值C17H15O2[M+H]+m/z 251.1067,实测值251.1070.
化合物I-8:按通用方法C制备得无色油状物，产率为98％。1H NMR(400MHz,CDCl3)δ:8.69(m,1H),8.05(m,3H),7.87(m,1H),7.70(m,1H),7.59(m,2H),7.48(d,J＝8.9Hz,1H),7.45–7.36(m,2H),7.20(d,J＝8.9Hz,1H),5.48(s,1H),3.99(s,3H).13C NMR(101MHz,CDCl3)δ:167.4,153.3,136.5,134.3,132.8,131.5,131.3,130.9,129.7,129.5,128.6,128.0,127.1,126.7,126.1,126.1,125.6,125.2,125.0,119.1,118.5,52.2.
HPLC分析(AD-H,5％IPA的环己烷溶液,1.0mL/min,254nm)测得90％ee:tR(major)＝14.9min,tR(minor)＝16.2min.HRMS(ESI)计算值C22H15O3[M-H]-m/z327.1027,实测值327.1023.
化合物I-9:按通用方法C制备得无色油状物，产率为86％。1H NMR(400MHz,CDCl3)δ:7.99(d,J＝8.4Hz,1H),7.93(m,3H),7.71–7.39(m,5H),7.30(m,2H),7.25(m,2H),3.66(m,1H),3.46–3.05(m,1H),2.99–2.15(m,2H),0.68m,3H),0.50–0.24(m,3H).13C NMR(101MHz,CDCl3)δ:169.9,135.6,134.2,133.9,133.3,132.9,132.7,132.1,129.6,128.6,128.5,128.3,128.1,127.8,127.6,127.3,127.1,126.8,126.7 126.3,126.2,126.1,125.7,125.6,125.4,124.4,123.5,123.2,42.7,42.5,37.5,14.0,13.6,11.5.
HPLC分析(AD-H,5％IPA的环己烷溶液,1.0mL/min,254nm)测得93％ee:tR(major)＝14.9min,tR(minor)＝16.9min.HRMS(ESI)计算值C25H24NO[M+H]+m/z354.1852,实测值354.1849.
化合物I-10:按通用方法B制备得棕色油状物，产率为81％。1H NMR(400MHz,CDCl3)δ:9.51(s,1H),8.13(m,1H),7.88–7.81(m,2H),7.71(m,1H),7.57(m,1H),7.41(m,2H),7.35–7.27(m,2H),7.22–7.16(m,1H),2.17(s,3H).13C NMR(101MHz,CDCl3)δ:192.2,143.9,134.8,134.3,133.4,133.4,131.9,131.6,128.5,128.4,128.3,128.1,127.4,126.6,125.8,125.3,21.0.
HPLC分析(OD-H,1％IPA的环己烷溶液,1.0mL/min,254nm)测得90％ee:tR(major)＝8.9min,tR(minor)＝9.5min.
化合物I-11:按通用方法B制备得黄色油状物，产率为75％。1H NMR(400MHz,CDCl3)δ:7.84(m,2H),7.49–7.41(m,3H),7.40–7.34(m,1H),7.30–7.25(m,1H),7.05(m,1H),6.93–6.85(m,2H),3.37(s,2H),2.29(s,3H).13C NMR(101MHz,CDCl3)δ:144.4,134.8,134.4,132.7,132.4,131.0,129.0,128.7,128.0,127.8,126.3,125.8,125.2,124.8,118.7,115.4,20.4.
HPLC分析(AD-H,1％IPA的环己烷溶液,1.0mL/min,220nm)测得85％ee:tR(major)＝11.9min,tR(minor)＝15.7min.HRMS(ESI)计算值C17H16N[M+H]+m/z 234.1277,实测值234.1278.
化合物I-12:按通用方法B制备得棕色油状物，产率为81％。1H NMR(400MHz,CDCl3)δ:7.92(d,J＝9.0Hz,1H),7.90–7.81(m,2H),7.65(m,1H),7.56(m,1H),7.40–7.31(m,4H),7.20–7.12(m,1H),4.24–4.00(m,2H),1.23(t,J＝7.0Hz,3H).13C NMR(101MHz,CDCl3)δ:153.5,136.1,136.0,133.9,132.9,131.5,130.3(q,J＝30.0Hz),129.7,128.6,127.8,127.5,126.75,126.3,126.2(q,J＝5.1Hz),125.2,124.1(q,J＝275.2Hz),123.5,114.2,64.6,14.9.19F NMR(376MHz,CDCl3)δ:-60.8.
HPLC分析(AD-H,1％IPA的环己烷溶液,1.0mL/min,254nm)测得91％ee:tR(major)＝4.5min,tR(minor)＝6.4min.HRMS(EI)计算值C19H15OF3[M]+m/z 316.1075,实测值316.1067.
化合物I-13:按通用方法A制备得白色固体，产率为89％。1H NMR(400MHz,CDCl3)δ:8.20(dd,J＝8.4,1.1Hz,1H),7.85(m,2H),7.53–7.42(m,2H),7.39–7.33(m,1H),7.30–7.22(m,3H),7.19(m,2H),7.15–7.08(m,1H),2.07(s,3H).13C NMR(101MHz,CDCl3)δ:158.4(d,J＝252.5Hz),135.4,133.9(d,J＝4.7Hz),133.7,133.5(d,J＝4.7Hz),132.1,128.7,127.9(d,J＝5.3Hz),127.5(d,J＝8.0Hz),127.2,126.3(d,J＝2.0Hz),126.2,126.1,126.1,125.0,124.0(d,J＝16.4Hz),120.9(d,J＝5.3Hz),109.5,109.3,20.7.19F NMR(376MHz,CDCl3)δ:-60.8.
HPLC分析(OJ-H,1％IPA的环己烷溶液,1.0mL/min,254nm)测得92％ee:tR(minor)＝16.4min,tR(major)＝25.9min.HRMS(EI)计算值C21H15OF[M]+m/z 286.1158,实测值286.1159.
化合物I-14:按通用方法A制备得黄色固体，产率为90％。1H NMR(400MHz,CDCl3)δ:8.65(d,J＝8.8Hz,1H),8.18(m,1H),8.05(d,J＝9.1Hz,1H),7.92(d,J＝8.2Hz,1H),7.86(m,1H),7.68(m,1H),7.59(m,1H),7.48(d,J＝9.1Hz,1H),7.37(m,1H),7.35–7.27(m,2H),7.11(d,J＝8.5Hz,1H),3.79(s,3H).13C NMR(101MHz,CDCl3)δ:154.6,147.3,135.7,134.1,134.0132.8,130.3,130.1,129.1,129.0,128.1,126.9,125.6,125.0,124.1,123.9,123.8,122.6,121.8,113.4,56.6.
HPLC分析(AD-H,1％IPA的环己烷溶液,1.0mL/min,254nm)测得97％ee:tR(major)＝10.0min,tR(minor)＝12.0min.HRMS(EI)计算值C21H15NO3[M]+m/z 329.1052,实测值329.1045.
化合物I-15:按通用方法A制备得无色油状物，产率为95％。1H NMR(400MHz,CDCl3)δ:8.40(m,1H),8.07(d,J＝7.3Hz,1H),7.93(m,2H),7.70(m,1H),7.52(d,J＝8.5Hz,1H),7.48–7.43(m,2H),7.43–7.39(m,1H),7.35(d,J＝8.4Hz,1H),7.29–7.24(m,1H),7.05(d,J＝8.5Hz,1H),2.11(s,3H).13C NMR(101MHz,CDCl3)δ:143.9,134.4,134.2,132.8,132.8,132.5,132.5,132.0,128.7,128.7,128.5,128.1,127.9,127.1,126.9,126.5,125.7,125.7,125.3,118.1,109.9,20.6.
HPLC分析(OJ-H,1％IPA的环己烷溶液,1.0mL/min,254nm)测得95％ee:tR(minor)＝16.4min,tR(major)＝25.9min.HRMS(EI)计算值C22H15N[M]+m/z 293.1204,实测值293.1214.
化合物I-16:按通用方法C制备得无色油状物，产率为99％。1H NMR(400MHz,CDCl3)δ:8.49(d,J＝1.8Hz,1H),8.04(d,J＝9.0Hz,1H),7.88(dd,J＝8.9,1.8Hz,1H),7.45(d,J＝9.0Hz,1H),7.40–7.36(m,2H),7.34(m,2H),7.18(m,1H),3.89(s,3H),2.70(s,3H),2.00(s,3H).13C NMR(101MHz,CDCl3)δ:197.9,155.9,137.6,135.9,135.5,132.4,131.1,130.8,130.6,130.0,127.9,127.8,125.8,125.5,124.6,124.5,114.0,56.4,26.7,19.8.
HPLC分析(OD-H,5％IPA的环己烷溶液,1.0mL/min,254nm)测得95％ee:tR(minor)＝7.7min,tR(major)＝8.3min.HRMS(ESI)计算值C20H19O2[M+H]+m/z290.1380,实测值291.1379.
化合物I-17:按通用方法A，使用1-萘基-三氟甲磺酸酯(55.2mg,0.2mmol,1.0equiv)和2-甲氧基-1-萘硼酸(48.5mg,0.24mmol,1.2equiv)，制备得无色油状物，产率为97％。1H NMR(400MHz,CDCl3)δ:8.03–7.92(m,3H),7.88(m,1H),7.63(m,1H),7.50–7.42(m,3H),7.34(m,2H),7.31–7.26(m,1H),7.23(dd,J＝6.6,1.4Hz,1H),7.17(m,1H),3.77(s,3H).13C NMR(101MHz,CDCl3)δ:154.6,134.6,134.3,133.7,133.0,129.5,129.0,128.5,128.2,127.8,127.8,126.4,126.2,125.9,125.7,125.6,125.5,123.6,123.3,113.9,56.8.
HPLC分析(AD-H,1％IPA的环己烷溶液,1.0mL/min,220nm)测得96％ee:tR(major)＝6.2min，tR(minor)＝7.6min.
化合物I-18:
按通用方法A，使用1-溴-2-甲氧基萘(47.4mg,0.2mmol,1.0equiv)和2-甲基苯硼酸(32.6mg,0.24mmol,1.2equiv)以及0.5mol％催化剂，制备得无色油状物，产率为97％。1H NMR(400MHz,CDCl3)δ:7.94(d,J＝9.0Hz,1H),7.91–7.84(m,1H),7.44–7.30(m,7H),7.26–7.22(m,1H),3.88(s,3H),2.06(s,3H).13C NMR(101MHz,CDCl3)δ:153.8,137.7,136.2,133.6,131.0,129.9,129.1,129.1,128.0,127.6,126.5,125.7,125.2,124.6,123.6,113.7,56.7,56.7,19.9.
HPLC分析(AD-H,1％IPA的环己烷溶液,1.0mL/min,254nm)测得93％ee:tR(major)＝4.3min,tR(minor)＝5.0min.
化合物I-18:
按通用方法A，使用1-溴-2-甲氧基萘(47.4mg,0.2mmol,1.0equiv)和4,4,5,5-四甲基-2-(2-甲基苯基)-1,3,2-二氧杂环戊硼烷(52.3mg,0.24mmol,1.2equiv)以及0.5mol％催化剂，制备得无色油状物，产率为99％，94％ee。
化合物I-18:
按通用方法A，使用1-溴-2-甲氧基萘(47.4mg,0.2mmol,1.0equiv)和5,5-二甲基-2-(2-甲基苯基)-1,3,2-二氧杂环己硼烷(49.0mg,0.24mmol,1.2equiv)以及0.5mol％催化剂，制备得无色油状物，产率为91％，93％ee。
化合物I-18:
按通用方法B，使用1-溴-2-甲氧基萘(47.4mg,0.2mmol,1.0equiv)和(2-甲基苯基)三氟硼酸钾(79.2mg,0.4mmol,2.0equiv)，制备得无色油状物，产率为98％，90％ee。
化合物I-19:按通用方法A，使用4,4,5,5-四甲基-2-(2-甲基-1-萘基)-1,3,2-二氧杂环戊硼烷(53.6mg,0.2mmol,1.0equiv),1-溴异喹啉(83.2mg,0.4mmol,2.0equiv)以及2mol％催化剂，制备得无色油状物，产率为60％。1H NMR(400MHz,CDCl3)δ:8.73(d,J＝5.7Hz,1H),8.01–7.82(m,3H),7.75(d,J＝5.8Hz,1H),7.66(m,1H),7.47(d,J＝8.4Hz,1H),7.43–7.33(m,3H),7.25–7.19(m,1H),6.99(d,J＝8.5Hz,1H),2.10(s,3H).13C NMR(101MHz,CDCl3)δ:160.6,142.9,136.4,134.9,134.4,133.0,132.1,130.4,128.7,128.5,128.4,128.0,127.5,127.3,127.1,126.3,125.7,125.0,120.1,20.2.
HPLC分析(AD-H,5％IPA的环己烷溶液,1.0mL/min,254nm)测得90％ee:tR(major)＝10.3min,tR(minor)＝10.9min.HRMS(ESI)计算值C20H16N[M+H]+m/z 270.1277,实测值270.1283.
化合物I-21:按通用方法A，制备得无色油状物，产率为88％。1H NMR(400MHz,CDCl3)δ:9.06(d,J＝4.4Hz,1H),8.27(d,J＝8.5Hz,1H),7.90(m,2H),7.72(m,1H),7.49(d,J＝8.5Hz,1H),7.41(t,J＝7.6Hz,1H),7.37–7.30(m,2H),7.30–7.21(m,3H),7.08(d,J＝8.5Hz,1H),2.11(s,3H).13C NMR(101MHz,CDCl3)δ:150.3,148.5,147.1,133.9,133.2,132.5,131.9,129.8,129.7,128.6,128.4,128.0,128.0,127.0,126.5,126.0,125.7,125.2,122.8,20.5.
HPLC分析(AD-H,3％IPA的环己烷溶液,1.0mL/min,254nm)测得93％ee:tR(minor)＝11.9min,tR(major)＝18.2min.HRMS(ESI)计算值C20H16N[M+H]+m/z 270.1277,实测值270.1279.
化合物I-22:
按通用方法A，制备得黄色油状物，产率为94％。1H NMR(400MHz,CDCl3)δ:8.92(m,1H),8.25(d,J＝8.5Hz,1H),7.90(d,J＝8.3Hz,2H),7.85(m,1H),7.58–7.53(m,1H),7.52–7.44(m,2H),7.44–7.38(m,1H),7.23(m,1H),7.18(m,1H),7.10(d,J＝8.5Hz,1H),2.10(s,3H).13C NMR(101MHz,CDCl3)δ:150.5,148.6,137.9,134.6,134.6,134.3,133.4,132.0,129.3,129.1,128.6,128.6,128.4,128.1,128.0,127.8,126.2,126.0,125.1,121.3,20.6.
HPLC分析(AD-H,3％IPA的环己烷溶液,1.0mL/min,254nm)测得94％ee:tR(minor)＝10.2min,tR(major)＝11.1min.HRMS(ESI)计算值C20H16N[M+H]+m/z 270.1277,实测值270.1276.
化合物I-22:
按通用方法A，制备得黄色油状物，产率为87％，94％ee。
化合物I-23:按通用方法A，制备得无色油状物，产率为91％。1H NMR(400MHz,CDCl3)δ:9.36(s,1H),8.35(d,J＝5.9Hz,1H),8.08(d,J＝8.2Hz,1H),8.02(d,J＝9.0Hz,1H),7.89(d,J＝8.2Hz,1H),7.76(t,J＝7.6Hz,1H),7.67(d,J＝7.0Hz,1H),7.45(d,J＝9.1Hz,1H),7.35(t,J＝7.5Hz,1H),7.31–7.21(m,1H),7.13(m,2H),3.77(s,3H).13C NMR(101MHz,CDCl3)154.7,152.9,143.2,135.7,134.0,133.9,132.9,130.2,129.1,129.0,128.1,127.4,127.1,126.8,125.0,123.8,121.2,119.0 113.5 56.6.
HPLC分析(AD-H,5％IPA的环己烷溶液,1.0mL/min,254nm)测得95％ee:tR(major)＝17.8min,tR(minor)＝19.6min.HRMS(ESI)计算值C20H16NO[M+H]+m/z 286.1226,实测值286.1227.
化合物I-24:按通用方法A，制备得无色油状物，产率为84％。1H NMR(400MHz,CDCl3)δ:8.70(s,1H),8.57(d,J＝5.7Hz,1H),8.04–7.89(m,3H),7.85(t,J＝7.7Hz,1H),7.78(d,J＝5.8Hz,1H),7.53(t,J＝7.7Hz,2H),7.44(t,J＝7.5Hz,1H),7.31–7.26(m,1H),7.13(d,J＝8.5Hz,1H),2.16(s,3H).13C NMR(101MHz,CDCl3)δ:151.2,143.1,138.6,136.3,134.6,133.9,133.5,132.0,130.4,129.4,128.6,128.3,128.0,127.7,126.3,126.3125.9,125.1,120.8,20.7.
HPLC分析(AD-H,5％IPA的环己烷溶液,1.0mL/min,254nm)测得94％ee:tR(minor)＝8.8min,tR(major)＝10.0min.HRMS(ESI)计算值C20H16N[M+H]+m/z 270.1277,实测值270.1278.
化合物I-25:按通用方法A，制备得无色油状物，产率为82％。1H NMR(400MHz,CDCl3)δ:8.86(m,1H),8.27(m,1H),7.97(m,1H),7.92(d,J＝8.3Hz,2H),7.71(t,J＝7.5Hz,1H),7.66(m,1H),7.55(d,J＝8.4Hz,1H),7.45–7.36(m,2H),7.30–7.23(m,1H),7.20(d,J＝8.5Hz,1H),2.18(s,3H).13C NMR(101MHz,CDCl3)δ:150.6,147.2,139.3,136.4,135.9,134.2,133.5,132.1,131.7,128.7,128.7,128.0,127.8,127.7,126.4,126.2,125.7,124.6,121.1,20.9.
HPLC分析(IC,5％IPA的环己烷溶液,1.0mL/min,254nm)测得90％ee:tR(major)＝11.4min,tR(minor)＝12.0min.HRMS(ESI)计算值C20H16ON[M+H]+m/z 270.1277,实测值270.1279.
化合物I-26:按通用方法A，制备得无色油状物，产率为92％。H NMR(400MHz,CDCl3)δ:8.77(m,1H),8.29(d,J＝9.3Hz,1H),7.96(t,J＝7.7Hz,2H),7.70–7.58(m,2H),7.54–7.45(m,2H),7.42(m,1H),7.34–7.27(m,2H),7.16–7.05(m,1H),3.78(s,3H).13C NMR(101MHz,CDCl3)δ:154.7,148.1,143.7,133.8,133.7,133.2,132.8,130.7,129.3,128.6,128.4,128.2,126.1,125.9,125.5,122.9,121.3,116.8,56.7,56.7.
HPLC分析(AD-H,5％IPA的环己烷溶液,1.0mL/min,254nm)测得96％ee:tR(minor)＝13.1min,tR(major)＝14.4min.HRMS(ESI)计算值C20H16NO[M+H]+m/z286.1226,实测值286.1226.
化合物I-27:按通用方法A，制备得无色油状物，产率为98％。1H NMR(400MHz,CDCl3)δ:8.92(m,1H),8.25(d,J＝8.5Hz,1H),8.00(d,J＝9.1Hz,1H),7.95–7.82(m,2H),7.68(m,1H),7.56–7.49(m,1H),7.44(d,J＝9.1Hz,1H),7.38–7.28(m,1H),7.27–7.22(m,2H),7.22–7.10(m,2H),3.75(s,3H).13C NMR(101MHz,CDCl3)δ:154.6,150.2,148.4,135.0,134.7,134.2,130.0,129.3,129.1,129.0,129.0,128.2,128.0,126.7,125.1,123.8,121.4,121.1,113.4,56.6,56.5.
HPLC分析(AD-H,5％IPA的环己烷溶液,1.0mL/min,254nm)测得95％ee:tR(minor)＝14.0min,tR(major)＝15.0min.HRMS(ESI)计算值C20H16NO[M+H]+m/z 286.1226,实测值286.1230.
化合物I-28:按通用方法A，制备得黄色油状物，产率为79％。1H NMR(400MHz,CDCl3)δ:8.96–8.84(m,1H),8.21(d,J＝8.5Hz,1H),7.95(d,J＝9.0Hz,1H),7.90–7.79(m,2H),7.68(m,1H),7.50(d,J＝7.0Hz,1H),7.39(d,J＝9.0Hz,1H),7.32(t,J＝7.4Hz,1H),7.26–7.21(m,1H),7.19(m,1H),7.15(d,J＝8.5Hz,1H),4.01(m,2H),1.02(t,J＝7.0Hz,3H).13C NMR(101MHz,CDCl3)δ:154.0,150.2,148.5,135.2,134.8,134.3,129.9,129.2,129.1,128.9,128.2,128.0,126.7,125.2,123.8,122.3,120.9,115.2,65.1,14.9.
HPLC分析(AD-H,5％IPA的环己烷溶液,1.0mL/min,254nm)测得92％ee:tR(major)＝11.1min,tR(minor)＝13.5min.HRMS(ESI)计算值C21H18NO[M+H]+m/z300.1383,实测值300.1383.
化合物I-29:按通用方法A，制备得黄色油状物，产率为94％。1H NMR(400MHz,CDCl3)δ:8.59(m,1H),7.91(d,J＝9.0Hz,1H),7.83(m,1H),7.49(m,1H),7.38–7.29(m,3H),7.23(m,2H),3.82(s,3H),2.25(s,3H).13C NMR(101MHz,CDCl3)δ:158.0,153.8,148.2,138.9,133.0,131.4,129.8,128.9,128.1,126.8,124.4,123.7,121.9,120.9,113.2,56.4,56.3,22.7.
HPLC分析(OJ-H,5％IPA的环己烷溶液,1.0mL/min,254nm)测得93％ee:tR(minor)＝9.8min,tR(major)＝16.0min.HRMS(ESI)计算值C17H16NO[M+H]+m/z 250.1226,实测值250.1226.
化合物I-30:按通用方法A，制备得黄色油状物，产率为79％。1H NMR(400MHz,CDCl3)δ:9.35(s,1H),8.79(s,1H),8.17(m,1H),8.06(m,1H),7.94–7.88(m,2H),7.56(m1H),7.50(d,J＝8.4Hz,1H),7.42(m,1H),7.26(m,1H),7.04(m,1H),2.11(s,3H).13C NMR(101MHz,CDCl3)δ:159.2,155.5,150.5,138.7,134.8,134.1,133.4,132.4,132.0,129.8,128.7,128.6,128.1,128.0,126.6,125.6,125.3,124.5,20.8.
HPLC分析(AD-H,1％IPA的环己烷溶液,1.0mL/min,220nm)测得94％ee:tR(minor)＝9.8min,tR(major)＝11.3min.HRMS(ESI)计算值C19H15N2[M+H]+m/z271.1230,实测值271.1233.
化合物I-31:按通用方法A，制备得白色固体，产率为93％。1H NMR(400MHz,CDCl3)δ:8.07(d,J＝9.0Hz,1H),7.95(d,J＝8.2Hz,1H),7.69(t,J＝7.7Hz,1H),7.53(d,J＝8.7Hz,2H),7.43–7.32(m,4H),7.30–7.22(m,2H),6.84(m,1H),6.76(d,J＝7.9Hz,1H),3.90(s,3H),3.78(s,3H).13C NMR(101MHz,CDCl3)δ:154.3,141.3,141.1,133.7,131.3,129.5,129.2,127.9,126.5,125.6,125.4,125.3,123.9,123.7,122.8,122.0,121.8,121.8,118.7,114.0,108.1,107.6,56.9,29.2.
HPLC分析(IC,1％IPA的环己烷溶液,1.0mL/min,220nm)测得99％ee:tR(minor)＝8.4min,tR(major)＝9.9min.HRMS(ESI)计算值C24H20NO[M+H]+m/z 338.1539,实测值338.1542.
化合物I-32:按通用方法A，制备得白色固体，产率为82％。1H NMR(400MHz,CDCl3)δ:7.90(d,J＝9.0Hz,1H),7.84–7.78(m,1H),7.37(d,J＝9.0Hz,1H),7.35–7.26(m,3H),7.25–7.19(m,2H),6.96(m,1H),6.71(d,J＝1.3Hz,1H),3.79(s,3H),3.74(s,3H),1.40(s,3H).13C NMR(101MHz,CDCl3)δ:154.5,137.5,134.9,129.4,129.0,128.7,127.7,127.4,127.3,126.2,126.0,124.8,123.4,121.4,121.4,113.7,111.0,108.5,56.9,32.7,10.6.
HPLC分析(AD-H,1％IPA的环己烷溶液,1.0mL/min,230nm)测得90％ee:tR(major)＝8.8min,tR(minor)＝12.1min.HRMS(ESI)计算值C21H20NO[M+H]+m/z302.1539,实测值302.1546.
化合物I-33:按通用方法A，制备得无色油状物，产率为97％。1H NMR(400MHz,CDCl3)δ:8.01(m,1H),7.90(t,J＝8.8Hz,2H),7.52(t,J＝7.7Hz,2H),7.44(m,1H),7.37–7.28(m,4H),6.73(m,1H),2.21(s,3H).13C NMR(101MHz,CDCl3)δ:140.0,139.6,136.4,135.2,133.9,133.0,132.1,128.7,127.9,127.7,126.3,126.2,126.1,126.0,125.0,124.4,123.6,121.7,20.7.
HPLC分析(OJ-H,1％IPA的环己烷溶液,1.0mL/min,220nm)测得86％ee:tR(minor)＝8.4min,tR(major)＝11.7min.HRMS(EI)计算值C15H14S[M]+m/z 274.0816,实测值274.0820.
化合物I-34:按通用方法B，制备得白色固体，产率为98％。1H NMR(400MHz,CDCl3)δ:8.88(m,1H),8.75(m,1H),8.25(d,J＝9.3Hz,1H),8.20(d,J＝8.5Hz,1H),7.81(m,1H),7.63(d,J＝9.4Hz,1H),7.59(m),7.45(m,2H),7.19(dd,J＝8.5,4.2Hz,1H),7.12(dd,J＝8.6,4.1Hz,1H),3.75(s,3H).13C NMR(101MHz,CDCl3)δ:154.7,150.4,148.5,148.4,143.9,134.3,133.6,133.3,131.3,129.6,129.2,129.2,129.1,128.0,121.6,121.2,121.2,116.5,56.6.
HPLC分析(AD-H,10％IPA的环己烷溶液,1.0mL/min,230nm)测得95％ee:tR(minor)＝19.9min,tR(major)＝26.3min.HRMS(ESI)计算值C19H15N2O[M+H]+m/z 287.1179,实测值287.1182.
化合物I-35:按通用方法A，制备得白色固体，产率为57％。1H NMR(400MHz,CDCl3)δ:7.97(d,J＝9.0Hz,2H),7.86(d,J＝8.1Hz,2H),7.45(d,J＝9.0Hz,2H),7.31(t,J＝7.4Hz,2H),7.24–7.16(m,2H),7.10(d,J＝8.5Hz,2H),3.76(s,6H).13C NMR(101MHz,CDCl3)δ:155.1,134.2,129.5,129.4,128.1,126.4,125.4,123.6,119.7,114.4,57.1.
HPLC分析(IC,1％IPA的环己烷溶液,1.0mL/min,280nm)测得96％ee:tR(major)＝8.3min,tR(minor)＝9.5min.
化合物I-36:按通用方法A，制备得白色固体，产率为62％。1H NMR(400MHz,CDCl3)δ:7.91(d,J＝9.0Hz,1H),7.86–7.75(m,3H),7.36(dd,J＝14.9,9.0Hz,2H),7.28–7.21(m,2H),7.19–7.09(m,3H),7.07(m,4H),6.95–6.84(m,2H),5.04–4.89(m,2H),3.67(s,3H).13CNMR(101MHz,CDCl3)δ:155.1,154.2,137.7,134.3,134.2,129.6,129.5,129.4,129.3,128.3,128.1,128.0,127.4,126.9,126.5,126.4,125.6,125.5,123.9,123.6,121.0,119.6,116.4,114.0,56.8.
HPLC分析(IC,1％IPA的环己烷溶液,1.0mL/min,254nm)测得92％ee:tR(major)＝7.0min,tR(minor)＝9.1min.
化合物I-37:按通用方法A，制备得白色固体，产率为85％。1H NMR(400MHz,CDCl3)δ:7.90(d,J＝9.0Hz,1H),7.86–7.78(m,1H),7.30(m,5H),7.14(d,J＝7.6Hz,1H),7.03(t,J＝8.6Hz,1H),3.83(s,3H),1.97(s,3H).13C NMR(101MHz,CDCl3)δ:161.9,159.5,154.4,140.5,140.5,133.2,129.9,129.1,128.8,128.8,128.8,128.2,128.2,126.8,125.4,125.4,124.4,123.7,123.7,123.6,117.6,113.7,113.6,112.9,112.7,56.7,56.7,19.8,19.6.19F NMR(376MHz,CDCl3)δ:-113.9.
HPLC分析(AD-H,1％IPA的环己烷溶液,1.0mL/min,220nm)测得95％ee:tR(major)＝5.0min,tR(minor)＝6.5min.HRMS(EI)计算值C18H15OF[M]+m/z 266.1107,实测值226.1102.
化合物I-38:按通用方法A，制备得棕色固体，产率为54％。1H NMR(400MHz,CDCl3)8.77(m,1H),8.25(d,J＝9.3Hz,1H),7.99(d,J＝9.0Hz,1H),7.88(d,J＝8.2Hz,1H),7.68(d,J＝9.3Hz,1H),7.45(d,J＝9.0Hz,2H),7.33(m,1H),7.27–7.21(m,1H),7.13(m,1H),7.10–7.05(m,1H),3.79(s,3H),3.77(s,3H).13C NMR(101MHz,CDCl3)δ:155.2,155.1,148.3,144.3,134.0,133.7,130.8,130.0,129.3,129.2,128.2,126.7,125.0,123.8,121.4,119.4,118.2,117.4,114.1,56.9,56.9.
HPLC分析(AD-H,5％IPA的环己烷溶液,1.0mL/min,280nm)测得94％ee:tR(major)＝22.5min,tR(minor)＝27.5min.HRMS(ESI)calculated
化合物I-39:按通用方法A，使用1,4-二溴萘(57.2mg,0.2mmol,1.0equiv)，(2-甲氧基-1-萘基)硼酸(145.5mg,0.72mmol,3.6equiv)，氢氧化钾(56mg,1.0mmol,5.0equiv)，2mol％催化剂以及2mL叔丁醇，制备得白色固体，产率为74％。1H NMR(400MHz,CDCl3)δ:7.98(d,J＝9.0Hz,2H),7.87(d,J＝8.1Hz,2H),7.56(s,2H),7.47(d,J＝9.0Hz,2H),7.42(m,2H),7.37–7.32(m,3H),7.32–7.19(m,5H),3.82(s,6H).13C NMR(101MHz,CDCl3)δ:154.9,134.5,134.3,133.3,129.6,129.2,128.3,127.9,126.6,126.5,126.0,125.7,123.7,123.7,114.1,57.0.
HPLC分析(IC,1％IPA的环己烷溶液,1.0mL/min,220nm)测得>99％ee:tR(minor)＝8.0min,tR(major)＝16.0min.HRMS(ESI)计算值C32H25O2[M+H]+m/z 441.1849,实测值441.1857.
化合物I-40:按通用方法A，使用1,4-二溴萘(57.2mg,0.2mmol,1.0equiv)，(2-甲基-1-萘基)硼酸(133.9mg,0.72mmol,3.6equiv)，氢氧化钾(56mg,1.0mmol,5.0equiv)，2mol％催化剂以及2mL叔丁醇，制备得白色固体，产率为60％。1H NMR(400MHz,CDCl3)δ:7.95(d,J＝8.3Hz,5H),7.59(d,J＝8.2Hz,2H),7.54(s,2H),7.46(m,3H),7.39–7.34(m,3H),7.32(d,J＝4.0Hz,4H),2.31(s,6H).13C NMR(101MHz,CDCl3)δ:137.2,136.3,134.7,133.7,132.9,132.2,128.8,128.0,127.7,127.7,126.5,126.4,126.2,126.1,125.0,20.9.
HPLC分析(waters UPC)(OJ-3,20％CO2 in methanol,1.0mL/min,214nm)测得>99％ee:tR(major)＝24.0min,tR(minor)＝34.9min.
Claims (10)
1.一种如式IV或如式IV’所示化合物，其特征在于，其结构如下所示：
其中，Ar3a、Ar3b、Ar3c和Ar3d独立地为未取代或R3a-1取代的C6-C14的芳基；每个R3a-1独立地为C1-C4的烷基；
R7a、R7b、R7c、R8a、R8b和R8c独立地为氢或C1-C4的烷基；
R5和R6独立地为氢、C1-C4的烷基、卤素、
或C6-C10的芳基；其中，R5-1和R5-2独立地为氢或C1-C4的烷基；
为单键或双键；
或者，R5、R6和与其相连的碳原子一起形成
2.如权利要求1所述的如式IV或如式IV’所示化合物，其特征在于，当Ar3a、Ar3b、Ar3c和Ar3d独立地为R3a-1取代的C6-C14的芳基时，所述的R3a-1独立地为一个或多个，优选1、2、3或4个，当存在多个R3a-1时，所述的R3a-1可相同或不同；
和/或，当Ar3a、Ar3b、Ar3c和Ar3d独立地为未取代或R3a-1取代的C6-C14的芳基时，所述的C6-C14的芳基独立地为C6-C10的芳基，优选苯基或萘基，更优选苯基；
和/或，当R3a-1独立地为C1-C4的烷基时，所述的C1-C4的烷基独立地为甲基或叔丁基，优选叔丁基；
和/或，当R7a、R7b、R7c、R8a、R8b和R8c独立地为C1-C4的烷基时，所述的C1-C4的烷基为甲基；
和/或，当R5和R6独立地为卤素时，所述的卤素独立地为F、Cl、Br或I；
和/或，当R5和R6独立地为C6-C10的芳基时，所述的C6-C10的芳基独立地为苯基或萘基。
3.如权利要求2所述的如式IV或如式IV’所示化合物，其特征在于，当Ar3a、Ar3b、Ar3c和Ar3d独立地为R3a-1取代的C6-C14的芳基时，所述的R3a-1取代的C6-C10的芳基独立地为
和/或，Ar3a、Ar3b、Ar3c和Ar3d相同；
和/或，Ar3a、Ar3b、Ar3c和Ar3d相同，Ar3a、Ar3b、Ar3c和Ar3d为R3a-1取代的C6-C14的芳基；
和/或，R7a、R7c、R8a和R8c相同，R7b和R8b相同；
和/或，R7a、R7c、R8a和R8c为氢，R7b和R8b相同，R7b和R8b为C1-C4的烷基。
4.如权利要求1所述的如式IV或如式IV’所示化合物，其特征在于，所述的如式IV或如式IV’所示化合物为以下任一方案：
方案1：
Ar3a、Ar3b、Ar3c和Ar3d独立地为未取代或R3a-1取代的C6-C14的芳基；每个R3a-1独立地为C1-C4的烷基；
Ar3a、Ar3b、Ar3c和Ar3d相同；
R7a、R7c、R8a和R8c为氢，R7b和R8b独立地为C1-C4的烷基，且R7b和R8b相同；
R5和R6为氢；
为单键或双；
或者，R5和R6和与其相连的碳原子一起形成
方案2：
Ar3a、Ar3b、Ar3c和Ar3d独立地为R3a-1取代的C6-C14的芳基；每个R3a-1独立地为C1-C4的烷基；
Ar3a、Ar3b、Ar3c和Ar3d相同；
R7a、R7c、R8a和R8c为氢，R7b和R8b独立地为C1-C4的烷基，且R7b和R8b相同；
R5和R6为氢；
为单键或双键；
或者，R5和R6和与其相连的碳原子一起形成
方案3：
Ar3a、Ar3b、Ar3c和Ar3d独立地为R3a-1取代的C6-C14的芳基；每个R3a-1独立地为C1-C4的烷基，优选叔丁基；
Ar3a、Ar3b、Ar3c和Ar3d相同；
R7a、R7c、R8a和R8c为氢，R7b和R8b独立地为C1-C4的烷基，且R7b和R8b相同；
R5和R6为氢；
为单键；
方案4：所述的如式IV或如式IV’所示化合物为以下任一结构：
5.一种所述的化合物IV-1或化合物IV-3的晶型，其特征在于，在使用辐射源为Ga-Kα的单晶X射线衍射光谱中，
所述的化合物IV-1的单晶属斜方晶系，空间群为P212121，其晶胞参数：
α＝90°，
β＝90°，
γ＝90°，晶胞体积
晶胞内不对称单位数Z＝4；所述的化合物IV-1的单晶参数优选为：
所述的化合物IV-3的单晶属斜方晶系，空间群为P212121，其晶胞参数：
α＝90°，
β＝90°，
γ＝90°，晶胞体积
晶胞内不对称单位数Z＝4；所述的化合物IV-3的单晶参数优选为：
6.一种如式IV或如式IV’所示化合物的制备方法，其包括以下步骤：有机溶剂中，在碱的作用下，将如式V或如式V’所示化合物与如式VI所示化合物进行如下所示的反应，即可；
其中，Ar3a、Ar3b、Ar3c、Ar3d、R5、R6、R7a、R7b、R7c、R8a、R8b、R8c和
如权利要求1-4中任一项所述。
7.一种化合物1的制备方法，其特征在于，其包括以下步骤：溶剂中，在钯复合物和碱的作用下，将如式II所示化合物和如式III所示化合物进行如下所示的偶联反应，即可；所述的化合物1为如式I所示化合物或如式I’所示化合物；
其中，
X为Cl、Br、I、OTs或OTf；
Y为B(OH)2、BPin、Bneo或BF3K；
Ar1和Ar2独立地为C6-C14的芳基、或“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基；
Z1、Z2、Z3、W1、W2和W3独立地为N或CR；
每个R、R1、R2、R3和R4独立地为氢、羟基、醛基、氨基、硝基、氰基、卤素、未取代或R1-1取代的C1-C4的烷基、未取代或R1-2取代的C1-C4的烷氧基、未取代或R1-3取代的C6-C14的芳基、未取代或R1-4取代的“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的C5-C14的杂芳基、
每个R1-1、R1-2、R1-3和R1-4独立地为卤素、C1-C4的烷基、C1-C4的烷氧基、或C6-C14的芳基；
每个R1-5独立地为羟基、C1-C4的烷基或C1-C4的烷氧基；
每个R1-6和R1-7独立地为氢或C1-C4的烷基；
或者，R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成未取代或Ra取代的C6-C14的芳基、或未取代或Rb取代的“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基；
每个Ra和Rb独立地为羟基、醛基、氨基、硝基、氰基、卤素、未取代或Ra-1取代的C1-C4的烷基、未取代或Ra-2取代的C1-C4的烷氧基、
每个Ra-1和Ra-2独立地为卤素、C1-C4的烷基、C1-C4的烷氧基、或C6-C14的芳基；
每个Ra-3独立地为羟基、C1-C4的烷基或C1-C4的烷氧基；
每个Ra-4和Ra-5独立地为氢或C1-C4的烷基；
所述的钯复合物为如式IV或如式IV’所示化合物，
其中，Ar3a、Ar3b、Ar3c、Ar3d、R5、R6、R7a、R7b、R7c、R8a、R8b、R8c和
如权利要求1-4中任一项所述；
当钯复合物为
时，所述的化合物1为如式I所示化合物；
当钯复合物为
时，所述的化合物1为如式I’所示化合物。
8.如权利要求7所述的化合物1的制备方法，其特征在于，当Ar1为C6-C14的芳基时，所述的C6-C14的芳基为C6-C10的芳基，优选苯基或萘基，更优选苯基；
和/或，当Ar1为“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基时，所述的5-14元的杂芳基为5-6元的单环杂芳基、或、6-14元的稠杂芳基，优选5-6元的单环杂芳基；所述的5-6元的单环杂芳基优选呋喃基、噻吩基、吡咯基、吡啶基、哒嗪基、嘧啶基或吡嗪基，更优选吡啶基；
和/或，当Ar2为C6-C14的芳基时，所述的C6-C14的芳基为C6-C10的芳基，优选苯基或萘基，更优选苯基；
和/或，当Ar2为“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基时，所述的5-14元的杂芳基为5-6元的单环杂芳基、或、6-14元的稠杂芳基，优选5-6元的单环杂芳基；所述的5-6元的单环杂芳基优选呋喃基、噻吩基、吡咯基、吡啶基、哒嗪基、嘧啶基或吡嗪基，更优选吡啶基；
和/或，当R、R1、R2、R3和R4独立地为卤素时，所述的卤素独立地为F、Cl、Br或I，优选F；
和/或，当R、R1、R2、R3和R4独立地为R1-1取代的C1-C4的烷基时，所述的R1-1独立地为一个或多个，优选1、2或3个，当存在多个R1-1时，所述的R1-1可相同或不同；
和/或，当R、R1、R2、R3和R4独立地为未取代或R1-1取代的C1-C4的烷基时，所述的C1-C4的烷基为甲基；
和/或，当R、R1、R2、R3和R4独立地为R1-2取代的C1-C4的烷氧基时，所述的R1-2独立地为一个或多个，优选1、2或3个，当存在多个R1-2时，所述的R1-2可相同或不同；
和/或，当R、R1、R2、R3和R4独立地为未取代或R1-2取代的C1-C4的烷氧基时，所述的C1-C4的烷氧基独立地为甲氧基或乙氧基；
和/或，当R、R1、R2、R3和R4独立地为R1-3取代的C6-C14的芳基时，所述的R1-3独立地为一个或多个，优选1、2、3或4个，当存在多个R1-3时，所述的R1-3可相同或不同；
和/或，当R、R1、R2、R3和R4独立地为未取代或R1-3取代的C6-C14的芳基时，所述的C6-C14的芳基独立地为C6-C10的芳基，优选苯基或萘基；
和/或，当R1-1、R1-2、R1-3和R1-4独立地为卤素时，所述的卤素独立地为F、Cl、Br或I，优选F；
和/或，当R1-1、R1-2、R1-3、R1-4、R1-5、R1-6和R1-7独立地为C1-C4的烷基时，所述的C1-C4的烷基为甲基；
和/或，当R1-1、R1-2、R1-3、R1-4和R1-5独立地为C1-C4的烷氧基时，所述的C1-C4的烷氧基独立地为甲氧基或乙氧基；
和/或，当R1-1、R1-2、R1-3、R1-4独立地为C6-C14的芳基时，所述的C6-C14的芳基独立地为C6-C10的芳基，优选苯基；
和/或，当R1-5、R1-6和R1-7独立地为C1-C4的烷基时，所述的C1-C4的烷基独立地为甲基或乙基；
和/或，当R1-5为C1-C4的烷氧基时，所述的C1-C4的烷氧基为甲氧基或乙氧基；
和/或，当R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成Ra取代的C6-C14的芳基时，所述的Ra独立地为一个或多个，优选1、2或3个，当存在多个Ra时，所述的Ra可相同或不同；
和/或，当R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成未取代或Ra取代的C6-C14的芳基时，所述的C6-C14的芳基为C6-C10的芳基，优选苯基或萘基；
和/或，当R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成Rb取代的“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基时，所述的Rb独立地为一个或多个，优选1、2或3个，当存在多个Rb时，所述的Rb可相同或不同；
和/或，当R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成未取代或Rb取代的“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基时，所述的5-14元的杂芳基为5-6元的单环杂芳基或6-14元的稠杂芳基，优选5-6元的单环杂芳基；所述的5-6元的单环杂芳基优选呋喃基、噻吩基、吡咯基、吡啶基、嘧啶基、哒嗪基或吡嗪基，更优选噻吩基、吡咯基、吡啶基或嘧啶基；所述的6-14元的稠杂芳基优选6-10元的稠杂芳基，更优选吲哚基、异吲哚基、喹啉基、异喹啉基，进一步优选吲哚基；
和/或，当Ra和Rb独立地为卤素时，所述的卤素独立地为F、Cl、Br或I；
和/或，当Ra和Rb独立地为Ra-1取代的C1-C4的烷基时，所述的Ra-1独立地为一个或多个，优选1、2或3个，当存在多个Ra-1时，所述的Ra-1可相同或不同；
和/或，当Ra和Rb独立地为Ra-2取代的C1-C4的烷氧基时，所述的Ra-2独立地为一个或多个，优选1、2或3个，当存在多个Ra-2时，所述的Ra-2可相同或不同；
和/或，当Ra-1和Ra-2独立地为卤素时，所述的卤素独立地为F、Cl、Br或I；
和/或，当Ra-1、Ra-2、Ra-3、Ra-4和Ra-5独立地为C1-C4的烷基时，所述的C1-C4的烷基独立地为甲基或乙基；
和/或，当Ra-1、Ra-2和Ra-3独立地为C1-C4的烷氧基时，所述的C1-C4的烷氧基为甲氧基；
和/或，当Ra-1和Ra-2独立地为C6-C14的芳基时，所述的C6-C14的芳基为C6-C10的芳基，优选苯基。
9.如权利要求7所述的化合物1的制备方法，其特征在于，所述的如式I所示化合物或如式I’所示化合物为以下任一方案：
方案1：
X为Cl、Br或OTf；
Y为B(OH)2、BPin、Bneo或BF3K；
Ar1和Ar2独立地为C6-C14的芳基；
Z1、Z2、Z3、W1、W2和W3独立地为N或CR；
每个R、R1、R2、R3和R4独立地为氢、羟基、醛基、氨基、硝基、氰基、卤素、未取代或R1-1取代的C1-C4的烷基、未取代或R1-2取代的C1-C4的烷氧基、或未取代或R1-3取代的C6-C14的芳基；
每个R1-1、R1-2、R1-3和R1-4独立地为卤素、C1-C4的烷基、或C1-C4的烷氧基；
每个R1-5独立地为C1-C4的烷基或C1-C4的烷氧基；
每个R1-6和R1-7独立地为氢或C1-C4的烷基；
或者，R1、R2与其相连的碳原子、和/或、R3、R4与其相连的碳原子一起独立地形成未取代或Ra取代的C6-C14的芳基、或未取代或Rb取代的“杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个”的5-14元的杂芳基；
每个Ra和Rb独立地为羟基、醛基、氨基、硝基、氰基、卤素、未取代的C1-C4的烷基、未取代的C1-C4的烷氧基、或
每个Ra-3独立地为C1-C4的烷基或C1-C4的烷氧基；
方案2：所述的如式I或式I’所示化合物为以下任一结构：
10.如权利要求7所述的化合物1的制备方法，其特征在于，所述的溶剂为有机溶剂、或有机溶剂和水的混合溶剂；所述的有机溶剂优选醇类溶剂、芳烃类溶剂和醚类溶剂中的一种或多种，更优选醇类溶剂和/或芳烃类溶剂；所述的醇类溶剂优选乙醇、异丙醇和叔丁醇中的一种或多种，更优选叔丁醇；所述的芳烃类溶剂优选甲苯；所述的醚类溶剂优选四氢呋喃(THF)；当所述的溶剂为有机溶剂和水的混合溶剂时，所述的有机溶剂和水的体积比优选5:1-10:1，更优选8:1-10:1；
和/或，所述的碱为碱金属氢氧化物、碱金属碳酸盐、碱金属磷酸盐和碱金属醇盐中的一种或多种，优选碱金属氢氧化物；所述的碱金属氢氧化物优选氢氧化钾；所述的碱金属碳酸盐优选碳酸钾和/或碳酸铯；所述的碱金属磷酸盐优选磷酸钾；所述的碱金属醇盐优选甲醇钾和/或叔丁醇钾，更优选叔丁醇钾；
和/或，所述的如式III所示化合物与所述的如式II所示化合物的摩尔比为1:1-5:1，优选1:1-2:1；
和/或，所述的碱与所述的如式II所示化合物的摩尔比为1:1-:1，优选1:1-3:1；
和/或，所述的如式II所示化合物在所述的溶剂中的摩尔浓度为0.1-0.5mol/L，优选0.1-0.3mol/L；
和/或，所述的钯复合物与所述的如式II所示化合物的摩尔比为1:10-1:500，优选1:50-1:200；
和/或，所述的偶联反应温度为30-60℃；
和/或，所述的偶联反应的时间为24-48h。
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