CN112430249A - Metal complex and preparation method thereof - Google Patents
Metal complex and preparation method thereof Download PDFInfo
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- CN112430249A CN112430249A CN202011302489.XA CN202011302489A CN112430249A CN 112430249 A CN112430249 A CN 112430249A CN 202011302489 A CN202011302489 A CN 202011302489A CN 112430249 A CN112430249 A CN 112430249A
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- Prior art keywords
- alkyl
- group
- radical
- aryl
- substituted
- Prior art date
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 24
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- -1 C2-C20Alkenyl radical Chemical class 0.000 claims description 121
- 125000000217 alkyl group Chemical group 0.000 claims description 101
- 150000003254 radicals Chemical class 0.000 claims description 51
- 125000001072 heteroaryl group Chemical group 0.000 claims description 47
- 125000003118 aryl group Chemical group 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 125000003107 substituted aryl group Chemical group 0.000 claims description 17
- 125000005843 halogen group Chemical group 0.000 claims description 16
- 239000003446 ligand Substances 0.000 claims description 15
- 125000006735 (C1-C20) heteroalkyl group Chemical group 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 12
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 12
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 9
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 8
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 7
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 150000003464 sulfur compounds Chemical class 0.000 claims description 6
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 125000005561 phenanthryl group Chemical group 0.000 claims description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese 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
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- ORBBTCHHNMWMCP-UHFFFAOYSA-K cycloocta-1,5-diene trichloroiridium Chemical class [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1 ORBBTCHHNMWMCP-UHFFFAOYSA-K 0.000 claims description 2
- SGSFNZOKVYTGRR-UHFFFAOYSA-L cycloocta-1,5-diene;diiodoplatinum Chemical compound [I-].[I-].[Pt+2].C1CC=CCCC=C1 SGSFNZOKVYTGRR-UHFFFAOYSA-L 0.000 claims description 2
- RXPAYNWWOUGGHI-UHFFFAOYSA-K cycloocta-1,5-diene;rhodium(3+);trichloride Chemical class Cl[Rh](Cl)Cl.C1CC=CCCC=C1 RXPAYNWWOUGGHI-UHFFFAOYSA-K 0.000 claims description 2
- 125000004989 dicarbonyl group Chemical group 0.000 claims description 2
- VVAOPCKKNIUEEU-PHFPKPIQSA-L dichloro(cycloocta-1,5-diene)platinum(ii) Chemical compound Cl[Pt]Cl.C\1C\C=C/CC\C=C/1 VVAOPCKKNIUEEU-PHFPKPIQSA-L 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- PFAGKWKLTYQJPZ-UHFFFAOYSA-K gold(3+) trichlorite Chemical compound [Au+3].Cl(=O)[O-].Cl(=O)[O-].Cl(=O)[O-] PFAGKWKLTYQJPZ-UHFFFAOYSA-K 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- QJDUDPQVDAASMV-UHFFFAOYSA-M sodium;ethanethiolate Chemical compound [Na+].CC[S-] QJDUDPQVDAASMV-UHFFFAOYSA-M 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 8
- 150000005840 aryl radicals Chemical class 0.000 claims 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims 1
- 229940126062 Compound A Drugs 0.000 claims 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 claims 1
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 6
- 229940079593 drug Drugs 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 description 24
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 125000000304 alkynyl group Chemical group 0.000 description 16
- 125000003342 alkenyl group Chemical group 0.000 description 15
- 125000003545 alkoxy group Chemical group 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 10
- 125000002950 monocyclic group Chemical group 0.000 description 9
- 125000000753 cycloalkyl group Chemical group 0.000 description 8
- 125000003367 polycyclic group Chemical group 0.000 description 8
- 125000004434 sulfur atom Chemical group 0.000 description 8
- 125000000392 cycloalkenyl group Chemical group 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 6
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- 239000000460 chlorine Substances 0.000 description 2
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- 125000001309 chloro group Chemical group Cl* 0.000 description 2
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- 238000007405 data analysis Methods 0.000 description 2
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- 239000011737 fluorine Substances 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000000575 pesticide 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
- 230000008569 process Effects 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 2
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- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
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- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 1
- FKTXDTWDCPTPHK-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical group FC(F)(F)[C](F)C(F)(F)F FKTXDTWDCPTPHK-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- 238000006845 Michael addition reaction Methods 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
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- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
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- 125000004619 benzopyranyl group Chemical group O1C(C=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- FOBPTJZYDGNHLR-UHFFFAOYSA-N diphosphorus Chemical compound P#P FOBPTJZYDGNHLR-UHFFFAOYSA-N 0.000 description 1
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- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WBVXKNCGMRPEBW-UHFFFAOYSA-N hydroxy-(4-methylphenoxy)-(4-methylphenyl)sulfanyl-sulfanylidene-lambda5-phosphane Chemical compound C1=CC(C)=CC=C1OP(O)(=S)SC1=CC=C(C)C=C1 WBVXKNCGMRPEBW-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004346 phenylpentyl group Chemical group C1(=CC=CC=C1)CCCCC* 0.000 description 1
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- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
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- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000005888 tetrahydroindolyl group Chemical group 0.000 description 1
- 125000003039 tetrahydroisoquinolinyl group Chemical group C1(NCCC2=CC=CC=C12)* 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000000147 tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000004632 tetrahydrothiopyranyl group Chemical group S1C(CCCC1)* 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000005307 thiatriazolyl group Chemical group S1N=NN=C1* 0.000 description 1
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- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
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- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application belongs to the technical field of organic synthetic chemistry, and particularly relates to a metal complex and a preparation method thereof. The molecular structure general formula of the metal complex is shown as an instruction formula I; the metal complex is a complex of a chiral phosphorus-sulfur compound and a metal, has a typical high-functional group structure, such as a chiral quaternary carbon atom containing an electron-withdrawing group and an amino group, has a classical organic metal complex structure, widens the coordination of the phosphorus-sulfur compound, can expand organic asymmetric catalytic reaction, and has good application in the synthesis of a drug intermediate and the preparation of a functional material.
Description
Technical Field
The application belongs to the technical field of organic synthetic chemistry, and particularly relates to a metal complex and a preparation method thereof.
Background
Complexes with bidentate or tridentate ligand scaffolds are of interest for their wide application in organometallic complexes. To the first, after asymmetric synthesis applications have been discovered, chiral derivatives have received great attention among these compounds, and they have a wide range of application prospects in the fields of organic synthetic chemistry, biochemistry, asymmetric catalysis, pesticides, and medical research.
Metal complexes, in particular chiral cyclopalladated complexes, have been used primarily in cycloaddition and hydrogenation functionalization reactions during the last decade. These synthetically challenging diphosphorus and phosphorus-nitrogen bidentate ligands can form five-or six-membered ring chelates with the metal center, thereby avoiding catalyst poisoning. Optically pure Csp2-E type metal complexes can also be successfully used to catalyze asymmetric Michael addition reactions, Hayashi-Miyaura arylboronic acid additions, 3-single bond transfer heteroclaisen repps, ring opening reactions, and the like.
Currently, activation of Csp by carbon-hydrogen bonds is useful3-H, building pentapentacyclic palladium metal complexes. However, these methods suffer from a number of disadvantages, such as 1) a multi-heteroatom rich backbone has not been achieved; 2) biocompatible frameworks rich in trifluoromethyl and the like are not realized; 3) the framework of coordination of both teeth of the amide-containing and the phosphorus-sulfur compound has not been realized.
Disclosure of Invention
The application aims to provide a metal complex and a preparation method thereof, and aims to solve the technical problem of how to realize the complexation of a chiral phosphorus-sulfur compound and a metal.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a metal complex, wherein the molecular structure of the metal complex is represented by formula i:
wherein the content of the first and second substances,
R1、R2、R3and R5Are identical or different C1-C20Alkyl radical, C1-C20Heteroalkyl group, C3-C20Cycloalkyl radical, C3-C20Heterocycloalkyl radical, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C3-C20Cycloalkenyl radical, C3-C20Heterocycloalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, C3-C20Cycloalkynyl group, C3-C20Heterocycloalkynyl, C1-C20Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C)1-C20) Alkyl, heteroaryl (C)1-C20) Alkyl radical, C2-C20Alkenyl (C)1-C20) Alkyl radical, C2-C20Alkynyl (C)1-C20) Alkyl, cyano (C)1-C20) Alkyl and C1-C20Alkyloxycarbonyl (C)1-C20) Any one of alkyl groups;
R4is hydrogen atom, cyano, C1-C20Ester group, C1-C20Alkyl radical, C1-C20Heteroalkyl group, C1-C20Haloalkyl, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, aryl (C)1-C20) Alkyl radical, C2-C10Alkenyl (C)1-C20) Alkyl and C2-C10Alkynyl (C)1-C20) Any one of alkyl groups;
R6is a halogen atom, C1-C5Ester group, C1-C5Borate ester group, C1-C5Phosphate group and C1-C5Any one of sulfonate groups;
m is any one of palladium, iridium, rhodium, manganese, nickel, platinum, gold, lithium and copper.
The metal complex provided by the application is a complex of a chiral phosphorus-sulfur compound and a metal, has a typical high-functional group structure, such as a chiral quaternary carbon atom containing an electron-withdrawing group and an amino group, has a classical organic metal complex structure, widens the coordination of the phosphorus-sulfur compound, can expand organic asymmetric catalytic reaction, and has good application in the synthesis of a drug intermediate and the preparation of a functional material.
In a second aspect, the present application provides a method for preparing a metal complex, comprising the steps of:
providing a chiral beta-nitro phosphorus sulfur compound A and a carboxylic acid compound B;
adding the chiral beta-nitro-phosphorus-sulfur compound A into a reaction system containing reducing metal, hydrochloric acid or trimethylchlorosilane for reaction to obtain a chiral beta-amino-phosphorus-sulfur compound C;
adding the chiral beta-aminophosphonium sulfur compound C into a reaction system containing the carboxylic acid compound B, a condensing agent and an alkali reagent to react to obtain a chiral beta-amidophosphorothioic compound ligand D;
adding the chiral beta-amidophosphorothioic compound ligand D into a metal compound MR6Reacting in the reaction system to obtain a metal complex shown as a formula I;
the structural general formula of the compound is as follows:
wherein the content of the first and second substances,
R1、R2、R3and R5Are identical or different C1-C20Alkyl radical, C1-C20Heteroalkyl group, C3-C20Cycloalkyl radical, C3-C20Heterocycloalkyl radical, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C3-C20Cycloalkenyl radical, C3-C20Heterocycloalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, C3-C20Cycloalkynyl group, C3-C20Heterocycloalkynyl, C1-C20Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C)1-C20) Alkyl, heteroaryl (C)1-C20) Alkyl radical, C2-C20Alkenyl (C)1-C20) Alkyl radical, C2-C20Alkynyl (C)1-C20) Alkyl, cyano (C)1-C20) Alkyl and C1-C20Alkyloxycarbonyl (C)1-C20) Any one of alkyl groups;
R4is hydrogen atom, cyano, C1-C20Ester group, C1-C20Alkyl radical, C1-C20Heteroalkyl group, C1-C20Haloalkyl, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, aryl (C)1-C20) Alkyl radical, C2-C10Alkenyl (C)1-C20) Alkyl and C2-C10Alkynyl (C)1-C20) Any one of alkyl groups;
R6is a halogen atom, C1-C5Ester group, C1-C5Borate ester group, C1-C5Phosphate group and C1-C5Any one of sulfonate groups;
m is any one of palladium, iridium, rhodium, manganese, nickel, platinum, gold, lithium and copper.
The preparation method of the metal complex is a complex preparation method of a chiral phosphorus-sulfur compound and a metal complex, and comprises the steps of reducing a chiral beta-nitro phosphorus-sulfur compound A to obtain a chiral beta-amino phosphorus-sulfur compound C, condensing the chiral beta-amino phosphorus-sulfur compound C with a carboxylic acid compound B to obtain a chiral beta-amido phosphorus-sulfur compound ligand D, and finally complexing the chiral beta-amido phosphorus-sulfur compound with the metal complex shown in the formula I. The preparation method simplifies the operation flow in the production process, has low requirement on reaction conditions, is safe and controllable in the reaction process, high in atom utilization rate and production efficiency and low in environmental pollution pressure, and therefore, the preparation method obviously reduces the production cost for preparing the complex of the chiral phosphorus-sulfur compound and the metal.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
The compounds and derivatives thereof referred to in the examples of the present invention are named according to the IUPAC (International Union of pure and applied chemistry) or CAS (chemical abstracts service, Columbus, Ohio) naming system. Accordingly, the groups of compounds specifically referred to in the examples of the present invention are illustrated and described as follows:
"alkoxy" refers to a straight or branched chain saturated aliphatic chain bonded to an oxygen atom, including, but not limited to, methoxy, ethoxy, propoxy, butoxy, isobutoxy, t-butoxy, and the like. (C)a-Cb) Alkoxy means any straight or branched, monovalent, saturated aliphatic chain in which an alkyl group containing "a" to "b" carbon atoms is bonded to an oxygen atom.
"alkyl" refers to a straight or branched chain saturated aliphatic chain, including but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, and the like.
"heteroalkyl" means a saturated aliphatic chain, straight or branched, containing at least one heteroatom linkage, such as, but not limited to, methylaminoethyl, methyloxypropyl, or other similar groups.
"alkenyl" refers to straight or branched chain hydrocarbons having one or more double bonds, including but not limited to, groups such as ethenyl, propenyl, and the like.
"Heteroalkenyl" means a straight or branched chain hydrocarbon with one or more double bonds containing at least one heteroatom linkage, including but not limited to, for example, vinylaminoethyl or other similar groups.
"alkynyl" refers to a straight or branched chain hydrocarbon with one or more triple bonds, including but not limited to, for example, ethynyl, propynyl, and the like.
"Heteroalkynyl" refers to a straight or branched chain hydrocarbon with one or more triple bonds containing at least one heteroatom linkage.
"aryl" refers to a cyclic aromatic hydrocarbon, which may be a monocyclic or polycyclic or fused ring aromatic hydrocarbon, including but not limited to, for example, phenyl, naphthyl, anthryl, phenanthryl, and the like.
"heteroaryl" means a monocyclic or polycyclic or fused ring aromatic hydrocarbon in which one or more carbon atoms have been replaced with a heteroatom such as nitrogen, oxygen, or sulfur. If the heteroaryl group contains more than one heteroatom, these heteroatoms may be the same or different. Heteroaryl groups include, but are not limited to, groups such as benzofuranyl, benzothienyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzopyranyl, furanyl, imidazolyl, indazolyl, indolizinyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxadiazolyl, oxazinyl, oxazolyl, phthalazinyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridine [3,4-b ] indolyl, pyridyl, pyrimidinyl, pyrrolyl, quinolizinyl, quinolyl, quinoxalinyl, thiadiazolyl, thiatriazolyl, thiazolyl, thienyl, triazinyl, triazolyl, xanthenyl, and the like.
"cycloalkyl" refers to a saturated monocyclic or polycyclic alkyl group, possibly fused to an aromatic hydrocarbon group. Cycloalkyl groups include, but are not limited to, groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indanyl, tetrahydronaphthyl, and the like.
"Heterocycloalkyl" means a saturated monocyclic or polycyclic alkyl group in which at least one carbon atom has been replaced by a heteroatom such as nitrogen, oxygen or sulfur, possibly fused to an aromatic hydrocarbon group. If the heterocycloalkyl group contains more than one heteroatom, these heteroatoms may be the same or different. Heterocycloalkyl groups include, but are not limited to, groups such as azepanyl, azetidinyl, indolinyl, morpholinyl, pyrazinyl, piperidinyl, pyrrolidinyl, tetrahydrofuryl, tetrahydroquinolinyl, tetrahydroindazolyl, tetrahydroindolyl, tetrahydroisoquinolinyl, tetrahydropyranyl, tetrahydroquinoxalinyl, tetrahydrothiopyranyl, thiazolidinyl, thiomorpholinyl, thioxanthyl, and the like.
"cycloalkenyl" refers to an unsaturated monocyclic or polycyclic alkenyl group with one or more double bonds, possibly fused to an aromatic hydrocarbon group, including but not limited to, cyclic ethenyl, cyclopropenyl, or other similar groups.
"Heterocycloalkenyl" means an unsaturated monocyclic or polycyclic alkenyl group with one or more double bonds, wherein at least one carbon atom is replaced by a heteroatom such as nitrogen, oxygen or sulfur, possibly fused to an aromatic hydrocarbon group. If the heterocycloalkyl group contains more than one heteroatom, these heteroatoms may be the same or different.
"cycloalkynyl" refers to an unsaturated monocyclic or polycyclic alkynyl group with one or more triple bonds, possibly fused to an aromatic hydrocarbon group, including, but not limited to, cycloalkynyl, cyclopropynyl, or other like groups.
"Heterocycloalkynyl" means an unsaturated monocyclic or polycyclic alkynyl group having one or more triple bonds in which at least one carbon atom is replaced by a heteroatom such as nitrogen, oxygen or sulfur, possibly fused to an aromatic hydrocarbon group. If a heterocyclic alkynyl group contains more than one heteroatom, these heteroatoms may be the same or different.
The hetero atom may be an oxygen atom, a nitrogen atom, a sulfur atom or the like.
In one aspect, embodiments of the present invention provide a metal complex, where a molecular structural general formula of the metal complex is as shown in formula i:
wherein the content of the first and second substances,
R1、R2、R3and R5Are identical or different C1-C20Alkyl radical, C1-C20Heteroalkyl group, C3-C20Cycloalkyl radical, C3-C20Heterocycloalkyl radical, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C3-C20Cycloalkenyl radical, C3-C20Heterocycloalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, C3-C20Cycloalkynyl group, C3-C20Heterocycloalkynyl, C1-C20Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C)1-C20) Alkyl, heteroaryl (C)1-C20) Alkyl radical, C2-C20Alkenyl (C)1-C20) Alkyl radical, C2-C20Alkynyl (C)1-C20) Alkyl, cyano (C)1-C20) Alkyl and C1-C20Alkyloxycarbonyl (C)1-C20) Any one of alkyl groups;
R4is hydrogen atom, cyano, C1-C20Ester group, C1-C20Alkyl radical, C1-C20Heteroalkyl group, C1-C20Haloalkyl, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, aryl (C)1-C20) Alkyl radical, C2-C10Alkenyl (C)1-C20) Alkyl and C2-C10Alkynyl (C)1-C20) Any one of alkyl groups;
R6is a halogen atom, C1-C5Ester group, C1-C5Borate ester group, C1-C5Phosphate group and C1-C5Any one of sulfonate groups;
m is any one of palladium, iridium, rhodium, manganese, nickel, platinum, gold, lithium and copper.
The metal complex provided by the application is a complex of a chiral phosphorus-sulfur compound and a metal, has a typical high-functional group structure, such as a chiral quaternary carbon atom containing an electron-withdrawing group and an amino group, has a classical organic metal complex structure, widens the coordination of the phosphorus-sulfur compound, can expand organic asymmetric catalytic reaction, and has good application in the synthesis of a drug intermediate and the preparation of a functional material.
R1、R2、R3And R5Are identical or different C1-C20Alkyl radical, C1-C20Heteroalkyl group, C3-C20Cycloalkyl radical, C3-C20Heterocycloalkyl radical, C2-C20An alkenyl group,C2-C20Heteroalkenyl, C3-C20Cycloalkenyl radical, C3-C20Heterocycloalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, C3-C20Cycloalkynyl group, C3-C20Heterocycloalkynyl, C1-C20Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C)1-C20) Alkyl, heteroaryl (C)1-C20) Alkyl radical, C2-C20Alkenyl (C)1-C20) Alkyl radical, C2-C20Alkynyl (C)1-C20) Alkyl, cyano (C)1-C20) Alkyl and C1-C20Alkyloxycarbonyl (C)1-C20) Any one of the alkyl radicals is R1、R2、R3And R5Each independently selected from the above groups, and may be the same or different.
When R is1、R2、R3Or R5Is selected from C1-C20When it is an alkyl group, in one embodiment, the group (C)1-C20) The alkyl group may be (C)1-C10) Alkyl, (C)1-C5) Alkyl, (C)1-C4) Alkyl, (C)1-C3) Alkyl, (C)1-C2) Alkyl groups, and the like. In certain embodiments, (C)1-C20) The alkyl group may be methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, and the like.
When R is1、R2、R3Or R5Is selected from (C)1-C20) When it is heteroalkyl, in one embodiment, (C) is1-C20) The heteroalkyl group may be (C)1-C10) Heteroalkyl group, (C)2-C5) Heteroalkyl group, (C)3-C4) Heteroalkyl groups and the like. In certain embodiments, the heteroatom may be an atom, a nitrogen atom, a sulfur atom, and the like.
When R is1、R2、R3Or R5Is selected from (C)3-C20) Cycloalkyl, in one embodiment, the (C)3-C20) The cycloalkyl group may be (C)3-C10) Cycloalkyl group, (C)3-C5) Cycloalkyl group, (C)3-C4) Cycloalkyl groups, and the like. In certain embodiments, (C)3-C20) Cycloalkyl groups may be cyclopropyl, cyclobutyl, cyclopentyl, and the like.
When R is1、R2、R3Or R5Is selected from (C)3-C20) When it is heterocycloalkyl, in one embodiment, (C) is3-C20) The heterocycloalkyl group may be (C)3-C10) Heterocycloalkyl group, (C)3-C10) Heterocycloalkyl group, (C)3-C5) Heterocycloalkyl group, (C)3-C4) Heterocycloalkyl, and the like. In certain embodiments, the heteroatom may be an oxygen atom, a nitrogen atom, a sulfur atom, and the like.
When R is1、R2、R3Or R5Is selected from (C)2-C20) Alkenyl, in one embodiment, the (C)2-C20) The alkenyl group may be (C)3-C10) Alkenyl, (C)3-C5) Alkenyl, (C)3-C4) Alkenyl, (C)2-C3) Alkenyl groups, and the like. In certain embodiments, (C)2-C20) The alkenyl group may be ethenyl, propenyl, butenyl, pentenyl, etc.
When R is1、R2、R3Or R5Is selected from (C)2-C20) (iii) when heteroalkenyl, in one embodiment, the (C)2-C20) The heteroalkenyl group can be (C)2-C10) Heteroalkenyl, (C)3-C10) Heteroalkenyl, (C)3-C5) Heteroalkenyl and the like. In certain embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.
When R is1、R2、R3Or R5Is selected from (C)3-C20) Cycloalkenyl group, in one embodiment, the (C)3-C20) Cycloalkenyl can be (C)3-C10) Cycloalkenyl group, (C)3-C5) Cycloalkenyl group, (C)3-C4) Cycloalkenyl groups, and the like. In certain embodiments, (C)3-C20) Cycloalkenyl can be cyclopropenyl, cyclobutenyl, cyclopentenyl and the like.
When R is1、R2、R3Or R5Is selected from (C)3-C20) When heterocycloalkenyl is present, in one embodiment, (C) is3-C20) The heterocycloalkenyl group may be (C)3-C10) Heterocycloalkenyl, (C)3-C5) Heterocycloalkenyl, (C)3-C4) Heterocycloalkenyl, and the like. In certain embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.
When R is1、R2、R3Or R5Is selected from (C)2-C20) Alkynyl, in one embodiment, (C)2-C20) Alkynyl may be (C)2-C10) Alkynyl, (C)3-C10) Alkynyl, (C)3-C5) Alkynyl, (C)3-C4) Alkynyl, (C)2-C3) Alkynyl and the like. In certain embodiments, (C)2-C20) The alkynyl group may be an ethynyl group, propynyl group, butynyl group, pentynyl group or the like.
When R is1、R2、R3Or R5Is selected from (C)2-C20) When heteroalkynyl is present, in one embodiment, (C) is2-C20) The heteroalkynyl can be (C)2-C10) Heteroalkynyl, (C)3-C10) Heteroalkynyl, (C)3-C5) Heteroalkynyl, (C)3-C4) Heteroalkynyl, and the like. In certain embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.
When R is1、R2、R3Or R5Is selected from (C)3-C20) When cycloalkynyl is present, in one embodiment, (C) is3-C20) The cycloalkynyl group can be (C)3-C10) Cycloalkynyl, (C)3-C5) Cycloalkynyl, (C)3-C4) Cycloalkynyl, and the like. In certain embodiments, (C)2-C20) Cycloalkynyl may beAnd cyclopropynyl, cyclobutynyl, cyclopentynyl and the like.
When R is1、R2、R3Or R5Is selected from (C)3-C20) When heterocycloalkynyl is present, in one embodiment, (C) is3-C20) The heterocycloalkynyl can be (C)3-C10) Heterocycloalkynyl, (C)3-C5) Heterocycloalkynyl, (C)3-C4) Heterocycloalkynyl, and the like. In certain embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.
When R is1、R2、R3Or R5Is selected from (C)1-C20) Alkoxy, in one embodiment, the (C)1-C20) The alkoxy group may be (C)1-C10) Alkoxy group, (C)1-C8) Alkoxy group, (C)1-C6) Alkoxy group, (C)1-C4) Alkoxy group, (C)1-C3) Alkoxy group, (C)1-C2) An alkoxy group. In certain embodiments, this (C)1-C20) Alkoxy groups may be, but are not limited to, methyloxy, ethyloxy, propyloxy, and the like.
When R is1、R2、R3Or R5When selected from aryl, the aryl group can be, but is not limited to, monocyclic aryl, polycyclic aryl, fused ring aryl. In one embodiment, the aryl group is a monocyclic aryl group. In certain embodiments, the aryl group may be C4-C14Aryl groups such as phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, and the like.
When R is1、R2、R3Or R5When selected from substituted aryl groups, the substituted aryl groups may be, but are not limited to, phenyl groups substituted singly or multiply in the ortho, meta, or para positions. Substituents include, but are not limited to, alkyl, substituted alkyl, aryl, substituted aryl, acyl, halo, alkoxy, nitro, -NR9R10、-NR9-CO-NR10、-OCONR9、-PR9R10、-SOR9、-SO2-R9、-SiR9R10R11、-BR9R10Wherein R is9、R10、R11R as defined above, which may be the same or different1、R2The groups shown. Wherein, when the substituent is an alkyl group, the alkyl group is exemplified by, but not limited to, methyl, ethyl, propyl, butyl, isobutyl; when the substituent is a substituted alkyl group, such as, but not limited to, trifluoromethyl, trichloromethyl, pentafluoroethyl, pentachloroethyl; when the substituent is halogen, such as, but not limited to, fluorine, chlorine, bromine, iodine; when the substituent is an alkoxy group, the alkoxy group is, for example, but not limited to, methyloxy, ethyloxy, propyloxy. In one embodiment, the substituted aryl group may be substituted (C)4-C14) Aryl, e.g. being cyano (C)1-C10) Alkyl radical (C)4-C8) Aryl, substituted (C)4-C8) And (4) an aryl group.
When R is1、R2、R3Or R5When selected from heteroaryl, in one embodiment, the heteroaryl may be (C)4-C14) Heteroaryl groups such as thienyl, thiazolyl, pyrrolyl, pyrazinyl, pyridyl, benzothiophene, and the like.
When R is1、R2、R3Or R5When selected from substituted heteroaryl, in one embodiment, the substituted heteroaryl may be substituted (C)4-C14) Heteroaryl, e.g. alkoxy-substituted furans, (C)3-C8) Heteroaryl substituted furans, aliphatic chain substituted thiophenes, and the like.
When R is1、R2、R3Or R5When selected from aryloxy, in one embodiment, the aryloxy may be C4-C14Aryloxy groups such as phenoxy, naphthoxy, anthracenoxy, phenanthrenoxy and the like.
When R is1、R2、R3Or R5When selected from heteroaryloxy, in one embodiment, the heteroaryloxy group may be C4-C14A heteroaryloxy group.
When R is1、R2、R3Or R5Selected from aryl (C)1-C20) When it is an alkyl group, in one embodiment, the aryl group (C)1-C20) The alkyl group may be C4-C14Aryl radical (C)1-C10) Alkyl radicals, e.g. phenyl (C)1-C10) Alkyl, phenyl (C)1-C5) Alkyl, phenyl (C)1-C4) Alkyl, phenyl (C)1-C3) Alkyl, phenyl (C)1-C2) Alkyl groups, and the like. In certain embodiments, aryl (C)1-C20) The alkyl group may be phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, phenylisobutyl, phenylpentyl, phenylisopentyl, phenylneopentyl, and the like.
When R is1、R2、R3Or R5Is selected from heteroaryl (C)1-C20) When alkyl, in one embodiment, the heteroaryl (C)1-C20) The alkyl group may be C4-C14Heteroaryl (C)1-C10) Alkyl radicals, e.g. heteroaryl (C)1-C10) Alkyl, heteroaryl (C)1-C5) Alkyl, heteroaryl (C)1-C4) Alkyl, heteroaryl (C)1-C3) Alkyl, heteroaryl (C)1-C2) Alkyl groups, and the like.
When R is1、R2、R3Or R5Is selected from (C)2-C20) Alkenyl (C)1-C20) When it is an alkyl group, in one embodiment, the group (C)2-C20) Alkenyl (C)1-C20) The alkyl group may be (C)2-C10) Alkenyl (C)1-C10) Alkyl, (C)2-C5) Alkenyl (C)1-C3) Alkyl groups, and the like.
When R is1、R2、R3Or R5Is selected from (C)2-C20) Alkynyl (C)1-C20) When it is an alkyl group, in one embodiment, the group (C)2-C20) Alkynyl (C)1-C20) The alkyl group may be (C)2-C10) Alkynyl (C)1-C10) Alkyl, (C)2-C5) Alkynyl (C)1-C3) Alkyl radicalAnd the like.
When R is1、R2、R3Or R5Is selected from cyano (C)1-C20) Alkyl, in one embodiment, the cyano (C)1-C20) The alkyl group may be cyano (C)1-C10) Alkyl, cyano (C)1-C5) Alkyl, cyano (C)1-C4) Alkyl, cyano (C)1-C3) Alkyl, cyano (C)1-C2) Alkyl groups, and the like. In certain embodiments, cyano (C)1-C20) The alkyl group may be cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, or the like.
When R is1、R2、R3Or R5Is selected from C1-C20Alkyl oxycarbonyl (C)1-C20) When it is alkyl, in one embodiment, the C1-C20Alkyl oxycarbonyl (C)1-C20) The alkyl group may be (C)1-C10) Alkyl oxycarbonyl (C)1-C10) Alkyl, (C)1-C5) Alkyl oxycarbonyl (C)1-C5) Alkyl, (C)1-C4) Alkyl oxycarbonyl (C)1-C4) Alkyl groups, and the like.
R4Is hydrogen atom, cyano, C1-C20Ester group, C1-C20Alkyl radical, C1-C20Heteroalkyl group, C1-C20Haloalkyl, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, aryl (C)1-C20) Alkyl radical, C2-C10Alkenyl (C)1-C20) Alkyl and C2-C10Alkynyl (C)1-C20) Any one of alkyl groups; further, R4Is a hydrogen atom, C1-C5Ester group, C1-C5Perhaloalkyl and C2-C10Any one of heteroalkyl groups. R4And R3Are not identical.
R6Is a halogen atomSeed, C1-C5Ester group, C1-C5Borate ester group, C1-C5Phosphate group and C1-C5Any one of sulfonate groups; further, R6Is a halogen atom.
M is any one of palladium, iridium, rhodium, manganese, nickel, platinum, gold, lithium and copper.
In one embodiment, in the metal complex of formula I, R5Is heteroaryl, specifically shown in the following structure, and X is a heteroatom, such as nitrogen atom, sulfur atom, oxygen atom, and the like.
The metal complex not only widens the coordination of phosphorus-sulfur compounds, but also constructs a chiral metal complex with potential by utilizing the coordination of amide and hetero atoms.
Specifically, in the metal complex, R1、R2And R3Is any one of aryl and substituted aryl which are the same or different, R4Is C1-C20Haloalkyl, R5Is heteroaryl, R6Is a halogen atom, C1-C5Ester group, C1-C5Borate ester group, C1-C5Phosphate group and C1-C5Any one of sulfonate groups. Wherein, R is1、R2And R3Wherein, the aryl group is selected from at least one of phenyl, naphthyl, anthryl, phenanthryl and fluorenyl, the substituted aryl group is selected from at least one of substituted phenyl, substituted naphthyl, substituted anthryl, substituted phenanthryl and substituted fluorenyl, and the R is5Is a nitrogen atom-containing heteroaryl group. In the substituted aryl group, the substituent is selected from the group consisting of a halogen atom, a hydroxyl group, an amino group, a nitro group, a sulfo group, a cyano group, an acyl group, an ester group and (C)1-C10) Alkyl, (C)6-C14) Aryl and (C)4-C14) At least one heteroaryl group. When R is4Is C1-C20When halogenated with alkylIn one embodiment, the (C)1-C20) The haloalkyl group may be halo (C)1-C10) Alkyl radicals, e.g. monohalogenated C1-C3Alkyl, dihalo C1-C3Alkyl, trihalo C1-C3The alkyl group, wherein the halogen may be fluorine substituted, chlorine substituted, bromine substituted or iodine substituted, etc. For example, perfluoroalkyl groups such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, and the like may be mentioned.
Further, in the metal complex, R1Is (C)1-C5) Alkyl-substituted phenyl, R2Is (C)1-C5) Alkyl-substituted phenyl, R3Is phenyl, R4Is C1-C5Perhaloalkyl radical, R5Is pyridine, R6Is a halogen atom.
In a preferred embodiment, the metal complex has a skeleton containing biocompatible groups such as amide, trifluoromethyl and the like, so that a complex of a chiral phosphorus-sulfur compound with potential application and a metal is obtained, and the designability and application prospect of the compound are greatly expanded.
In another aspect, a process for preparing a metal complex as hereinbefore described, which process comprises the steps of:
s01: providing a chiral beta-nitro phosphorus sulfur compound A and a carboxylic acid compound B;
s02: adding the chiral beta-nitro-phosphorus-sulfur compound A into a reaction system containing reducing metal, hydrochloric acid or trimethylchlorosilane for reaction to obtain a chiral beta-amino-phosphorus-sulfur compound C;
s03: adding the chiral beta-aminophosphonium sulfur compound C into a reaction system containing the carboxylic acid compound B, a condensing agent and an alkali reagent to react to obtain a chiral beta-amidophosphorothioic compound ligand D;
s04: sulfurizing the chiral beta-phosphoramidateAddition of Complex ligand D to Metal-containing Compound MR6Reacting in the reaction system to obtain a metal complex shown as a formula I;
the structural general formula of the compound is as follows:
wherein the content of the first and second substances,
R1、R2、R3and R5Are identical or different C1-C20Alkyl radical, C1-C20Heteroalkyl group, C3-C20Cycloalkyl radical, C3-C20Heterocycloalkyl radical, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C3-C20Cycloalkenyl radical, C3-C20Heterocycloalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, C3-C20Cycloalkynyl group, C3-C20Heterocycloalkynyl, C1-C20Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C)1-C20) Alkyl, heteroaryl (C)1-C20) Alkyl radical, C2-C20Alkenyl (C)1-C20) Alkyl radical, C2-C20Alkynyl (C)1-C20) Alkyl, cyano (C)1-C20) Alkyl and C1-C20Alkyloxycarbonyl (C)1-C20) Any one of alkyl groups;
R4is hydrogen atom, cyano, C1-C20Ester group, C1-C20Alkyl radical, C1-C20Heteroalkyl group, C1-C20Haloalkyl, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, aryl (C)1-C20) Alkyl radical, C2-C10Alkenyl (C)1-C20) Alkyl and C2-C10Alkynyl (C)1-C20) Any one of alkyl groups;
R6is a halogen atom, C1-C5Ester group, C1-C5Borate ester group, C1-C5Phosphate group and C1-C5Any one of sulfonate groups;
m is any one of palladium, iridium, rhodium, manganese, nickel, platinum, gold, lithium and copper.
The preparation method of the metal complex is a complex preparation method of a chiral phosphorus-sulfur compound and a metal complex, and comprises the steps of reducing a chiral beta-nitro phosphorus-sulfur compound A to obtain a chiral beta-amino phosphorus-sulfur compound C, condensing the chiral beta-amino phosphorus-sulfur compound C with a carboxylic acid compound B to obtain a chiral beta-amido phosphorus-sulfur compound ligand D, and finally complexing the chiral beta-amido phosphorus-sulfur compound with the metal complex shown in the formula I. The preparation method simplifies the operation flow in the production process, has low requirement on reaction conditions, is safe and controllable in the reaction process, high in atom utilization rate and production efficiency and low in environmental pollution pressure, and therefore, the preparation method obviously reduces the production cost for preparing the complex of the chiral phosphorus-sulfur compound and the metal.
In the step S01, the chiral β -nitrophosulfur compound a and the carboxylic acid compound B can be prepared according to a conventional method in the art, and can be obtained directly from the market.
For chiral beta-nitro phosphorus sulfur compound A and carboxylic acid compound B, and metal compound MR6In (b) each R1、R2、R3、R4、R5And R6In order to correspond to R in the finally obtained metal complex shown as the formula I1、R2、R3、R4、R5And R6R is a hydrogen atom1、R2、R3、R4、R5And R6Specific choices have been set forth above in detail.
In the above step S02 and step S03, the molar ratio of the chiral β -nitrophosphorus sulfide compound a to the carboxylic acid compound B is (0.1-20): (0.1-20). Specifically, the molar ratio of the chiral beta-nitro phosphorus sulfur compound A, the carboxylic acid compound B, the beta-amino phosphorus sulfur compound C and the chiral beta-amido phosphorus sulfur compound ligand D is (0.1-20): (0.1-20): (0.2-40): (1-100).
Further, the chiral beta-nitro-phosphorus-sulfur compound A is added into a reaction system containing reducing metal, hydrochloric acid or trimethylchlorosilane, and the reaction temperature is 50-100 ℃. Adding the chiral beta-aminophosphonium sulfur compound C into a reaction system containing the carboxylic acid compound B, the condensing agent and the alkali reagent to react at the temperature of 25-100 ℃.
Further, the carboxylic acid compound B is:
the obtained chiral beta-amidophosphoric sulfur compound ligand D is as follows:
the metal complex finally prepared is:
further, the reducing metal is selected from at least one of iron powder, zinc powder and manganese powder: the condensing agent is selected from at least one of 2- (7-azobenzotriazol) -N, N, N ', N' -tetramethylurea hexafluorophosphate, benzotriazol-N, N, N ', N' -tetramethylurea hexafluorophosphate, dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride; the alkali reagent is at least one of lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1,5, 7-triazabicyclo (4.4.0) dec-5-ene, triethylamine, diisopropylethylamine, bistrimethylsilyl amino lithium, bistrimethylsilyl sodium, bistrimethylsilyl potassium, diisopropylamino lithium, n-butyl lithium, tert-butyl lithium, methyllithium, sodium methoxide, sodium ethoxide and sodium ethylmercaptide.
In the above step S04, the chiral beta-phosphoramidothio compound ligand D is added into the metal compound MR6The reaction temperature in the reaction system of (1) is 25 to 100 ℃.
Further, the metal compound MR6Is at least one of palladium dichloride, palladium acetate, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, bis (1, 5-cyclooctadiene) iridium tetrafluoroborate, 1, 5-cyclooctadiene iridium chloride dimer, bis (1, 5-cyclooctadiene) rhodium tetrafluoroborate, (1, 5-cyclooctadiene) rhodium chloride dimer, polymeric rhodium dicarbonyl chloride, manganese pentacarbonyl bromide, manganese pentacarbonyl chloride, bis- (1, 5-cyclooctadiene) nickel, nickel chloride, (1, 5-cyclooctadiene) platinum diiodide, (1, 5-cyclooctadiene) platinum dichloride, gold chloride, gold chlorite, copper dichloride, copper sulfate, ketone tetrafluoroborate, ketone hexafluorophosphate and lithium chloride.
In a word, the preparation method of the complex of the chiral phosphorus-sulfur compound and the metal is implemented by the steps of reducing, condensing, complexing with the metal and the like of the chiral beta-nitro phosphorus-sulfur compound; the preparation method has the advantages of simple process, low requirement on reaction conditions, safe and controllable reaction process, high atom utilization rate and production efficiency, and high efficiency in ensuring the enantioselectivity of the product. And the operation flow in the preparation and production process is simplified, the toxicity of the reaction residues is reduced to the minimum, the pollution to the environment in the production process is reduced, and the steps and the operation for removing the residues after the reaction can be simplified. In addition, reactant raw materials are very easy to obtain, and the reactants can be directly used for preparation production without additional modification before reaction, so that the operation steps are simplified, and the reaction route is shortened; obviously reduces the production cost. The preparation method for constructing the complex of the chiral phosphorus-sulfur compound and the metal can be widely applied to the research fields of organic synthetic chemistry, biochemistry, asymmetric catalysis, pesticides and medicines. The complex of the chiral phosphorus-sulfur compound and the metal complex has good application in the synthesis of a drug intermediate, the preparation of a functional material and a metal ligand or a complex, and can effectively reduce the economic cost for the preparation of the drug intermediate, the functional material and the metal ligand or the complex.
The following description will be given with reference to specific examples.
Example 1
Respectively providing a nitro phosphorus sulfur compound A1 and a carboxylic acid compound B1 represented by the following structural formulas to prepare a complex of a chiral phosphorus sulfur compound and a metal:
A1、
B1、
(1) preparation of beta-aminophosphonium sulphur compounds
The nitro phosphorus sulfur compound A1(0.1mmol) and zinc powder (0.7mmol) were dissolved in a mixed solvent of 0.6mL of methanol, 0.3mL of tetrahydrofuran and 0.6mL of hydrochloric acid (6M), and the mixture was refluxed at 80 ℃ and stirred overnight. The progress of the reaction was checked by TLC, when the reaction was complete, saturated aqueous sodium bicarbonate was slowly added dropwise to adjust the pH of the solution to 8, the solution was filtered through celite and extracted twice with dichloromethane, the combined organic phases were dried over anhydrous sodium sulfate for 1 hour and filtered, the organic phase was concentrated and then directly purified by silica gel column chromatography (methanol and dichloromethane as eluent) to give β -aminophosphazene compound C1, i.e. (S) - (3-amino-1, 1, 1-trifluoro-2-phenylpropan-2-yl) di-p-tolyl phosphorothioide in 77% yield and 95% ee. The structural formula of the (S) - (3-amino-1, 1, 1-trifluoro-2-phenylpropan-2-yl) di-p-tolyl phosphorus sulfide compound is shown as the following molecular structural formula C1:
the prepared beta-aminophosphonium sulfur compound C1 was subjected to characterization data analysis, and the results were:1H NMR(400MHz,CDCl3)δ7.82(dd,J＝12.6,8.1Hz,2H),7.58–7.49(m,2H),7.36–7.30(m,1H),7.30–7.25(m,2H),7.24–7.18(m,4H),7.08(dd,J＝8.3,3.2Hz,2H),3.83(dd,J＝5.6,3.3Hz,2H),2.39(s,3H),2.33(s,3H),1.33(s,2H).13C NMR(101MHz,CDCl3)δ142.66(d,J＝3.0Hz),142.45(d,J＝3.0Hz),134.25(d,J＝10.1Hz),133.87(d,J＝9.1Hz),130.45(q,J＝6.1Hz),130.17(d,J＝5.1Hz),128.84,128.65(q,J＝286.8Hz),128.52,128.20(d,J＝3.0Hz),126.30(d,J＝12.1Hz),125.49(d,J＝18.2Hz),93.01,44.26(q,J＝25.1Hz),29.82,21.55(d,J＝2.0Hz),21.47(d,J＝1.0Hz).31P NMR(162MHz,CDCl3)δ50.46.HRMS(ESI-TOF)[M+H]calculated for[C23H24F3NPS]+434.1319, applied 434.1315.HPLC (Chiralpak-IC-H column,80:20hexane/ethanol, flow rate:1.0mL/min): tmajor 9.679 min; tminor 18.555 min; this result further confirmed the molecular structure of the product as described above for molecular structure C1.
(2) Preparation of beta-phosphorothioates
The β -aminophosphothio compound C1(0.1mmol) was dissolved in 1.0mL of pretreated dichloromethane, and carboxylic acid compound B1, i.e., 2-picolinic acid (0.11mmol), 2- (7-azobenzotriazol) -N, N' -tetramethyluronium hexafluorophosphate (0.1mmol), and nitrogen, nitrogen-diisopropylethylamine (0.3mmol) were added thereto at room temperature, followed by stirring at room temperature overnight. The reaction was then quenched with water, the aqueous phase was extracted twice with dichloromethane, the combined organic phases were dried over anhydrous sodium sulfate for 1 hour and filtered, and the organic phase was concentrated and then directly purified by column chromatography on silica gel (ethyl acetate and petroleum ether as eluent) to give the β -phosphothioate compound D1, i.e. (S) -nitrogen- (2- (di-p-tolylthio-thiophosphate) -3,3, 3-trifluoro-2-phenylpropyl) pyridinamide in 84% yield and 94% ee. The structural formula of the (S) -N- (2- (di-p-tolyl thiophosphoryl) -3,3, 3-trifluoro-2-phenylpropyl) pyridinamide is shown as the following molecular structural formula D1:
the prepared beta-aminoacyl phosphorus sulfur compound D1 is analyzed by characterization data, and the result is that:1H NMR(400MHz,CDCl3)δ8.35(d,J＝4.4Hz,1H),8.31–8.24(m,1H),8.04(d,J＝7.8Hz,1H),7.85(dd,J＝12.7,8.2Hz,1H),7.70(m,J＝7.7,1.5Hz,1H),7.63(dd,J＝12.3,8.2Hz,1H),7.28(dd,J＝12.5,5.3Hz,1H),7.23–7.15(m,1H),7.12(dd,J＝8.0,2.8Hz,1H),4.81(dd,J＝13.5,7.3Hz,1H),4.53(dt,J＝14.9,5.0Hz,1H),2.34(d,J＝11.5Hz,1H).13C NMR(101MHz,CDCl3)δ164.27(s),149.27(s),148.23(s),142.89(d,J＝3.2Hz),142.84(d,J＝3.0Hz),137.30(s),134.32(d,J＝10.4Hz),134.01(d,J＝9.7Hz),130.22(s),129.90(d,J＝3.8Hz),128.90(d,J＝2.5Hz),128.77(d,J＝2.2Hz),128.07(d,J＝2.0Hz),126.33(s),126.26(s),125.49(d,J＝4.8Hz),124.67(s),122.21(s),61.34(dd,J＝38.3,21.8Hz),40.72(s),29.83(s),21.53(d,J＝2.1Hz).31P NMR(162MHz,CDCl3)δ51.46(s).HRMS(ESI-TOF)[M+H]calculated for[C29H27N2OF3PS+]+539.1528,observed 539.1526.HPLC(Chiralpak-IC-H column,85:15hexane/ethanol,flow rate:1.0mL/min):tmajor＝15.670 min；tminor17.472 min; this result further confirmed the molecular structure of the product as described above for molecular structure D1.
(3) Metal complex of chiral phosphorus-sulfur compound and metal
Dissolving palladium dichloride (0.23mmol) and lithium chloride (0.92mmol) in a mixed solvent (2: 1, 100mL) of methanol and trichloromethane, and stirring for 30 minutes at normal temperature; beta-aminoacyl phosphorus sulfide D1(0.23mmol) is dissolved in a mixed solvent of methanol and chloroform (2: 1, 5mL), and then is dropwise added into the reaction system, and stirring is continued for 5 days at normal temperature. After the reaction is finished, the reaction liquid is dried and concentrated under reduced pressure, and then is directly separated and purified by silica gel column chromatography (ethyl acetate and petroleum ether are used as eluent) to obtain the target product metal complex I1, namely (S) - (N- (2- (p-tolyl phosphorothioacyl) -3,3, 3-trifluoro-2-phenylpropyl) pyridine carboxamide group) palladium chloride, yellow solid, the yield is 63 percent, and the ee value is 94 percent. The structural formula of the (S) - (N- (2- (p-tolyl phosphorothioacyl) -3,3, 3-trifluoro-2-phenylpropyl) pyridine carboxamide) palladium chloride is shown as the following molecular structural formula I1:
the product I1 prepared was subjected to characterization data analysis, which resulted in:1H NMR(400MHz,CDCl3)δ9.03(d,J＝5.4Hz,1H),8.21(dd,J＝13.3,8.2Hz,1H),7.95(m,J＝6.2Hz,1H),7.59(d,J＝7.5Hz,1H),7.47–7.33(m,1H),7.28(dd,J＝8.1,3.2Hz,1H),7.23(d,J＝8.6Hz,1H),7.18(t,J＝7.5Hz,1H),7.00(dd,J＝8.1,3.5Hz,1H),4.84–4.31(m,1H),2.38(s,1H),2.26(s,1H).13C NMR(101MHz,CDCl3)δ153.87(s),147.77(s),144.50(d,J＝3.2Hz),143.75(d,J＝3.1Hz),139.81–139.13(m),134.42(d,J＝11.1Hz),133.73(d,J＝9.4Hz),131.61(s),129.71(s),129.57(s),129.39(s),129.26(s),128.60–128.38(m),126.76(s),125.84(s),123.91(s),123.16(s),122.30(s).31P NMR(162MHz,CDCl3)δ62.26(s).HRMS(ESI-TOF)[M-Cl]calculated for[C29H25F3N2OPPdS]+643.0412,observed 643.0408.HPLC(Chiralpak-IC-H column,80:20 hexane/ethanol,flow rate:1.0mL/min):tmajor＝32.542min；tminor29.478 min; this result further confirmed the molecular structure of the product as described above for molecular structure I1.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A metal complex is characterized in that the molecular structure general formula of the metal complex is shown as formula I:
wherein the content of the first and second substances,
R1、R2、R3and R5Are identical or different C1-C20Alkyl radical, C1-C20Heteroalkyl group, C3-C20CycloalkanesBase, C3-C20Heterocycloalkyl radical, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C3-C20Cycloalkenyl radical, C3-C20Heterocycloalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, C3-C20Cycloalkynyl group, C3-C20Heterocycloalkynyl, C1-C20Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C)1-C20) Alkyl, heteroaryl (C)1-C20) Alkyl radical, C2-C20Alkenyl (C)1-C20) Alkyl radical, C2-C20Alkynyl (C)1-C20) Alkyl, cyano (C)1-C20) Alkyl and C1-C20Alkyloxycarbonyl (C)1-C20) Any one of alkyl groups;
R4is hydrogen atom, cyano, C1-C20Ester group, C1-C20Alkyl radical, C1-C20Heteroalkyl group, C1-C20Haloalkyl, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, aryl (C)1-C20) Alkyl radical, C2-C10Alkenyl (C)1-C20) Alkyl and C2-C10Alkynyl (C)1-C20) Any one of alkyl groups;
R6is a halogen atom, C1-C5Ester group, C1-C5Borate ester group, C1-C5Phosphate group and C1-C5Any one of sulfonate groups;
m is any one of palladium, iridium, rhodium, manganese, nickel, platinum, gold, lithium and copper.
2. The metal complex of claim 1, wherein R is1、R2、R3And R5Are identical or different C1-C10Alkyl radical, C1-C10Heteroalkyl group, C3-C10Cycloalkyl radical, C3-C10Heterocycloalkyl radical, C2-C10Alkenyl radical, C2-C10Heteroalkenyl, C3-C10Cycloalkenyl radical, C3-C10Heterocycloalkenyl, C2-C10Alkynyl, C2-C10Heteroalkynyl, C3-C10Cycloalkynyl group, C3-C10Heterocycloalkynyl, C1-C10Alkoxy radical, C4-C14Aryl, substituted (C)4-C14) Aryl radical, C4-C14Heteroaryl, substituted (C)4-C14) Heteroaryl group, C4-C14Aryloxy radical, C4-C14Heteroaryloxy radical, C4-C14Aryl radical (C)1-C10) Alkyl radical, C4-C14Heteroaryl (C)1-C10) Alkyl radical, C2-C10Alkenyl (C)1-C10) Alkyl radical, C2-C10Alkynyl (C)1-C10) Alkyl, cyano (C)1-C10) Alkyl and C1-C10Alkyloxycarbonyl (C)1-C10) Any one of alkyl groups; and/or the presence of a gas in the gas,
R4is a hydrogen atom, C1-C5Ester group, C1-C5Perhaloalkyl and C2-C10Any one of heteroalkyl groups; and/or the presence of a gas in the gas,
R6is a halogen atom.
3. The metal complex of claim 1, wherein R is1、R2And R3Is any one of aryl and substituted aryl which are the same or different, R4Is C1-C20Haloalkyl, R5Is heteroaryl.
4. The metal complex of claim 3, wherein R is1、R2And R3Wherein, the aryl group is selected from at least one of phenyl, naphthyl, anthryl, phenanthryl and fluorenyl, the substituted aryl group is selected from at least one of substituted phenyl, substituted naphthyl, substituted anthryl, substituted phenanthryl and substituted fluorenyl, and the R is5Is a nitrogen atom-containing heteroaryl group.
5. The metal complex according to claim 4, wherein the substituent of the substituted aryl group is selected from the group consisting of a halogen atom, a hydroxyl group, an amino group, a nitro group, a sulfo group, a cyano group, an acyl group, an ester group, and a group (C)1-C10) Alkyl, (C)6-C14) Aryl and (C)4-C14) At least one heteroaryl group.
6. The metal complex of claim 4, wherein R is1Is (C)1-C5) Alkyl-substituted phenyl, R2Is (C)1-C5) Alkyl-substituted phenyl, R3Is phenyl, R4Is C1-C5Perhaloalkyl radical, R5Is pyridine, R6Is a halogen atom.
7. A method for preparing a metal complex, comprising the steps of:
providing a chiral beta-nitro phosphorus sulfur compound A and a carboxylic acid compound B;
adding the chiral beta-nitro-phosphorus-sulfur compound A into a reaction system containing reducing metal, hydrochloric acid or trimethylchlorosilane for reaction to obtain a chiral beta-amino-phosphorus-sulfur compound C;
adding the chiral beta-aminophosphonium sulfur compound C into a reaction system containing the carboxylic acid compound B, a condensing agent and an alkali reagent to react to obtain a chiral beta-amidophosphorothioic compound ligand D;
adding the chiral beta-amidophosphorothioic compound ligand D into a metal compound MR6Reacting in the reaction system to obtain a metal complex shown as a formula I;
the structural general formula of the compound is as follows:
wherein the content of the first and second substances,
R1、R2、R3and R5Are identical or different C1-C20Alkyl radical, C1-C20Heteroalkyl group, C3-C20Cycloalkyl radical, C3-C20Heterocycloalkyl radical, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C3-C20Cycloalkenyl radical, C3-C20Heterocycloalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, C3-C20Cycloalkynyl group, C3-C20Heterocycloalkynyl, C1-C20Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C)1-C20) Alkyl, heteroaryl (C)1-C20) Alkyl radical, C2-C20Alkenyl (C)1-C20) Alkyl radical, C2-C20Alkynyl (C)1-C20) Alkyl, cyano (C)1-C20) Alkyl and C1-C20Alkyloxycarbonyl (C)1-C20) Any one of alkyl groups;
R4is hydrogen atom, cyano, C1-C20Ester group, C1-C20Alkyl radical, C1-C20Heteroalkyl group, C1-C20Haloalkyl, C2-C20Alkenyl radical, C2-C20Heteroalkenyl, C2-C20Alkynyl, C2-C20Heteroalkynyl, aryl (C)1-C20) Alkyl radical, C2-C10Alkenyl (C)1-C20) Alkyl and C2-C10Alkynyl (C)1-C20) Any one of alkyl groups;
R6is a halogen atom, C1-C5Ester group, C1-C5Borate ester group, C1-C5Phosphate group and C1-C5Any one of sulfonate groups;
m is any one of palladium, iridium, rhodium, manganese, nickel, platinum, gold, lithium and copper.
8. The method according to claim 7, wherein the molar ratio of the chiral β -nitrophosulfur compound A to the carboxylic acid compound B is (0.1-20): (0.1-20).
9. The method of claim 7, wherein the reducing metal is selected from at least one of iron powder, zinc powder, and manganese powder: and/or
The condensing agent is selected from at least one of 2- (7-azobenzotriazol) -N, N, N ', N' -tetramethylurea hexafluorophosphate, benzotriazol-N, N, N ', N' -tetramethylurea hexafluorophosphate, dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride; and/or
The alkali reagent is at least one of lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1,5, 7-triazabicyclo (4.4.0) dec-5-ene, triethylamine, diisopropylethylamine, bistrimethylsilyl amino lithium, bistrimethylsilyl sodium, bistrimethylsilyl potassium, diisopropylamino lithium, n-butyl lithium, tert-butyl lithium, methyllithium, sodium methoxide, sodium ethoxide and sodium ethylmercaptide; and/or
The metal compound MR6Is palladium dichloride, palladium acetate, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphonium) palladium, bis (1, 5-cyclooctadiene) iridium tetrafluoroborate, 1, 5-cyclooctadiene iridium chloride dimer, bis (1, 5-cyclooctadiene) rhodium tetrafluoroborate, (1, 5-cyclooctadiene) rhodium chloride dimer, polymeric rhodium dicarbonyl chloride, manganese pentacarbonyl bromide, manganese pentacarbonyl chloride, bis- (1, 5-cyclooctadiene) nickelAt least one of nickel chloride, (1, 5-cyclooctadiene) platinum diiodide, (1, 5-cyclooctadiene) platinum dichloride, gold chloride, gold chlorite, copper dichloride, copper sulfate, ketone tetrafluoroborate, ketone hexafluorophosphate, and lithium chloride.
10. The method of claim 7, wherein R is1、R2、R3And R5Are identical or different C1-C10Alkyl radical, C1-C10Heteroalkyl group, C3-C10Cycloalkyl radical, C3-C10Heterocycloalkyl radical, C2-C10Alkenyl radical, C2-C10Heteroalkenyl, C3-C10Cycloalkenyl radical, C3-C10Heterocycloalkenyl, C2-C10Alkynyl, C2-C10Heteroalkynyl, C3-C10Cycloalkynyl group, C3-C10Heterocycloalkynyl, C1-C10Alkoxy radical, C4-C14Aryl, substituted (C)4-C14) Aryl radical, C4-C14Heteroaryl, substituted (C)4-C14) Heteroaryl group, C4-C14Aryloxy radical, C4-C14Heteroaryloxy radical, C4-C14Aryl radical (C)1-C10) Alkyl radical, C4-C14Heteroaryl (C)1-C10) Alkyl radical, C2-C10Alkenyl (C)1-C10) Alkyl radical, C2-C10Alkynyl (C)1-C10) Alkyl, cyano (C)1-C10) Alkyl and C1-C10Alkyloxycarbonyl (C)1-C10) Any one of alkyl groups; and/or the presence of a gas in the gas,
R4is a hydrogen atom, C1-C5Ester group, C1-C5Perhaloalkyl and C2-C10Any one of heteroalkyl groups; and/or the presence of a gas in the gas,
R6is a halogen atom.
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Citations (3)
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| CN101020701A (en) * | 2007-03-16 | 2007-08-22 | 郑州大学 | Forcipated diimidazoline palladium compound and its application in Suzuki reaction |
| US20100292084A1 (en) * | 2009-05-14 | 2010-11-18 | Technion Research & Development Foundation Ltd. | Novel diarylphosphine- and dialkylphosphine-containing compounds, processes of preparing same and uses thereof as tridentate ligands |
| CN104513274A (en) * | 2013-09-29 | 2015-04-15 | 上海交通大学 | P chiral pincer compound and palladium coordination compound thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020701A (en) * | 2007-03-16 | 2007-08-22 | 郑州大学 | Forcipated diimidazoline palladium compound and its application in Suzuki reaction |
| US20100292084A1 (en) * | 2009-05-14 | 2010-11-18 | Technion Research & Development Foundation Ltd. | Novel diarylphosphine- and dialkylphosphine-containing compounds, processes of preparing same and uses thereof as tridentate ligands |
| CN104513274A (en) * | 2013-09-29 | 2015-04-15 | 上海交通大学 | P chiral pincer compound and palladium coordination compound thereof |
Non-Patent Citations (2)
| Title |
|---|
| DIANA V. ALEKSANYAN ET AL.: "Synthesis and complexing properties of phosphorus-substituted pyridine-2-carboxylic acid anilides" * |
| VLADIMIR A. KOZLOV ET AL.: "Effective Modular Assembling of Novel Ligands Starting from (Thio)Phosphorylated Anilines" * |
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