JP2018515515A - カイラルスピロ環ホスフィン−窒素−硫黄三座配位子およびその調製方法と応用 - Google Patents
カイラルスピロ環ホスフィン−窒素−硫黄三座配位子およびその調製方法と応用 Download PDFInfo
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- JP2018515515A JP2018515515A JP2017558681A JP2017558681A JP2018515515A JP 2018515515 A JP2018515515 A JP 2018515515A JP 2017558681 A JP2017558681 A JP 2017558681A JP 2017558681 A JP2017558681 A JP 2017558681A JP 2018515515 A JP2018515515 A JP 2018515515A
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- nitrogen
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- 239000003446 ligand Substances 0.000 title claims abstract description 59
- FBVGKIOCASRSER-UHFFFAOYSA-N P.[S].[N] Chemical compound P.[S].[N] FBVGKIOCASRSER-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- -1 transition metal salt Chemical class 0.000 claims abstract description 55
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 18
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 16
- 125000003003 spiro group Chemical group 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 229910052741 iridium Inorganic materials 0.000 claims description 11
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 6
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 6
- OGFKTAMJLKHRAZ-UHFFFAOYSA-N 2,2-dimethoxyacetaldehyde Chemical compound COC(OC)C=O OGFKTAMJLKHRAZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 125000001544 thienyl group Chemical group 0.000 claims description 6
- 150000004798 β-ketoamides Chemical class 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- 238000001308 synthesis method Methods 0.000 claims description 5
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 230000003213 activating effect Effects 0.000 claims description 3
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 2
- OFDISMSWWNOGFW-UHFFFAOYSA-N 1-(4-ethoxy-3-fluorophenyl)ethanamine Chemical compound CCOC1=CC=C(C(C)N)C=C1F OFDISMSWWNOGFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 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
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 239000011968 lewis acid catalyst Substances 0.000 claims description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 2
- ULWOJODHECIZAU-UHFFFAOYSA-N n,n-diethylpropan-2-amine Chemical compound CCN(CC)C(C)C ULWOJODHECIZAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- IVRIRQXJSNCSPQ-UHFFFAOYSA-N propan-2-yl carbonochloridate Chemical compound CC(C)OC(Cl)=O IVRIRQXJSNCSPQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006268 reductive amination reaction Methods 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012321 sodium triacetoxyborohydride Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 5
- 239000012018 catalyst precursor Substances 0.000 claims 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims 1
- 229910018286 SbF 6 Inorganic materials 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims 1
- 125000000101 thioether group Chemical group 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 52
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 12
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012043 crude product Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000002274 desiccant Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical group NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000007306 turnover Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- UJXIOVIFPTXDHU-UHFFFAOYSA-N 2-phenylethanethioyl chloride Chemical compound ClC(=S)CC1=CC=CC=C1 UJXIOVIFPTXDHU-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- 241000761456 Nops Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 108700041286 delta Proteins 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011982 enantioselective catalyst Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
Description
R2、R3、R4、R5は、それぞれ独立して、H、C1〜C10アルキル基、フェニル基、置換フェニル基、1−ナフチル基、2−ナフチル基、ヘテロアリール基またはベンジル基から選ばれ、前記のフェニル基における置換基がC1〜C10の炭化水素基、アルコキシ基であり、置換基数が1〜5であり、ヘテロアリール基がフリル基、チエニル基又はピリジル基であり;或いは、C1〜C10アルコキシ基であり;あるいは、R2〜R3、R4〜R5が結合してC3〜C7脂肪族環、芳香環になり;R2、R3、R4、R5が互いに同一であっても異なっていてもよく;
R6、R7は、それぞれ独立して、H、C1〜C10アルキル基、C1〜C10アルコキシ基、C1〜C10脂肪族アミン基から選ばれ、n=0〜3;或いは、n≧2の場合、隣接する2つのR6、R7が結合してC3〜C7脂肪族環または芳香環になってもよく、R6、R7が互いに同一であっても異なっていてもよく;
R8、R9は、それぞれ独立して、C1〜C10アルキル基、C1〜C10アルコキシ基、フェニル基、置換フェニル基、1−ナフチル基、2−ナフチル基、ヘテロアリール基またはベンジル基から選ばれ、前記のフェニル基における置換基がC1〜C10の炭化水素基、アルコキシ基であり、置換基数が1〜5であり、ヘテロアリール基がフリル基、チエニル基またはピリジル基であり;あるいは、R8、R9がC2〜C4の炭素鎖、窒素、酸素、硫黄を含む炭素鎖、芳香族環または複素芳香環を介して連結して環に形成してもよく;R8、R9が互いに同一であっても異なっていてもよい。)
(その中、式1、2、3、4におけるR1〜R9の意味が前述と同じであり、式2におけるXがH、Cl、Br、またはイミダゾリル基、あるいはOHであり;カイラルスピロジヒドロインデン骨格を有する式1で示す化合物は、従来文献に従って調製する(Jian−Bo Xie,Jian−Hua Xie,Xiao−Yan Liu,Wei−Ling Kong,Shen Li,Qi−Lin Zhou,J.Am.Chem.Soc.2010,132,4538;周其林、
(R)−N−(2−(フェニルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Ia)の合成
(R)−N−(2−(フェニルチオ)エチル)−7′−ジ−(3,5−ジメチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Ib)の合成
(R)−N−(2−(フェニルチオ)エチル)−7′−ジフェニルホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Ic)の合成
(R)−N−(2−(2,6−ジメチルフェニルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Id)の合成
(R)−N−(2−(3,5−ジメチルフェニルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Ie)の合成
(R)−N−(2−(4−メチルフェニルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(If)の合成
(R)−N−(2−(2−ナフチルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Ig)の合成
(R)−N−(2−(4−メトキシフェニルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Ih)の合成
Mp 124−126 oC,
(R)−N−(2−(2,6−ジクロロフェニルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Ii)の合成
Mp 78−80 oC,
(R)−N−(2−(4−クロロフェニルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Ij)の合成
(R)−N−(2−(4−トリフルオロメチルフェニルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Ik)の合成
(R)−N−(2−(エチルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Il)の合成
Mp 94−96 oC,
(R)−N−(2−(tert−ブチルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Im)の合成
Mp 152−155 oC,
(R)−N−(2−(シクロヘキシルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(In)の合成
Mp
(R)−N−(2−(ベンジルチオ)エチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(Io)の合成
Mp 47−49 oC,
(R)−N−((1,3−ジチアン−2−イル)メチル)−7−ジ−(3,5−ジ−tert−ブチルフェニル)ホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(IIa)の合成
(R)−N−((1,3−ジチアン−2−イル)メチル)−7−ジフェニルホスフィノ−7'−アミノ−1,1′−スピロジヒドロインデン(IIb)の合成
カイラルスピロ環ホスフィン−窒素−硫黄三座配位子のカルボニル化合物の不斉触媒水素化反応への応用。
Claims (19)
- 一般式Iまたは一般式IIを有する化合物、或いは、前記化合物のエナンチオマー、ラセミ体、またはその触媒的に許容される塩である、カイラルスピロ環ホスフィン−窒素−硫黄三座配位子。
R2、R3、R4、R5は、それぞれ独立して、H、C1〜C10アルキル基、フェニル基、置換フェニル基、1−ナフチル基、2−ナフチル基、ヘテロアリール基またはベンジル基から選ばれ、前記のフェニル基における置換基がC1〜C10の炭化水素基、アルコキシ基であり、置換基数が1〜5であり、ヘテロアリール基がフリル基、チエニル基又はピリジル基であり;或いは、C1〜C10アルコキシ基であり;あるいは、R2〜R3、R4〜R5が結合してC3〜C7脂肪族環、芳香環基になり;R2、R3、R4、R5が互いに同一であっても異なっていてもよく;
R6、R7は、それぞれ独立して、H、C1〜C10アルキル基、C1〜C10アルコキシ基、C1〜C10脂肪族アミン基から選ばれ、n=0〜3;或いは、n≧2の場合、隣接する2つのR6、R7が結合してC3〜C7脂肪族環または芳香環になってもよく、R6、R7が互いに同一であっても異なっていてもよく;
R8、R9は、それぞれ独立して、C1〜C10アルキル基、C1〜C10アルコキシ基、フェニル基、置換フェニル基、1−ナフチル基、2−ナフチル基、ヘテロアリール基またはベンジル基から選ばれ、前記のフェニル基における置換基がC1〜C10の炭化水素基、アルコキシ基であり、置換基数が1〜5であり、ヘテロアリール基がフリル基、チエニル基またはピリジル基であり;あるいは、R8、R9がC2〜C4の炭素鎖、窒素、酸素、硫黄を含む炭素鎖、芳香族環または複素芳香環を介して連結して環に形成してもよく;R8、R9が互いに同一であっても異なっていてもよい。) - カイラルスピロジヒドロインデン骨格を有する式1で示すラセミ体または光学活性な7−ジアリール/アルキルホスフィノ−7′−アミノ−1,1′−スピロジヒドロインデン類化合物を出発原料として、下記の反応式を経て調製すること、を特徴とする請求項1に記載のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子の合成方法。
(その中、式1、2、3およびIにおけるR1〜R9の意味が請求項1における記載と同じであり、式2におけるXがH、Cl、Br、またはイミダゾリル基、またはOHである。) - カイラルスピロジヒドロインデン骨格を有する式1で示すラセミ体または光学活性な7−ジアリール/アルキルホスフィノ−7′−アミノ−1,1′−スピロジヒドロインデン類化合物を出発原料として、下記の反応式を経て調製すること、を特徴とする請求項1に記載のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子の合成方法。
(その中、式1、4およびIIにおけるR1〜R9の意味が請求項1における記載と同じである。) - 有機溶媒とアルカリとの存在で、反応器にてまず式1を有する化合物を式2で示す化合物(XがHまたはOHではない)と2〜24時間反応させて式3で示す化合物を調製し、そして、式3で示す化合物を還元試薬で還元させて式Iで示すカイラルスピロ環ホスフィン−窒素−硫黄三座配位子を得る工程、あるいは、
有機溶媒と還元試薬との存在で、反応器にてまず式1を有する化合物を式2で示す化合物(XがHである)と2〜24時間反応させて直接に式Iで示すカイラルスピロ環ホスフィン−窒素−硫黄三座配位子を調製する工程、
を含むこと、を特徴とする請求項1または請求項2に記載のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子の合成方法。 - 前記式1で示す化合物と式2で示す化合物と使用される還元試薬とのモル比が1:1〜5:1〜10であり、反応温度が−20〜120oCであること、を特徴とする請求項4に記載の合成方法。
- 有機溶媒、アルカリとカルボキシル基を活性化する試薬の存在で、反応器にてまず式1を有する化合物を式2で示す化合物(XがOHである)と2〜24時間反応させて式3で示す化合物を調製し、そして、式3で示す化合物を還元試薬で還元させて式Iで示すカイラルスピロ環ホスフィン−窒素−硫黄三座配位子を得る工程を含むこと、を特徴とする請求項1または請求項2に記載のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子の合成方法。
- 前記式1で示す化合物と式2で示す化合物(XがOHである)と使用されるカルボキシル基を活性化する試薬と還元試薬とのモル比が1:1〜5:1〜10:1〜10であり、反応温度が−20〜120oCであること、を特徴とする請求項6に記載の合成方法。
- 有機溶媒と還元試薬との存在で、反応器にてまず式1を有する化合物をグリオキサールジメチルアセタールと還元アミノ化反応させて式4で示す化合物を調製し、そして、式4で示す化合物とメルカプタン(R8SHとR9SH)とをルイス酸の触媒で置換反応させて式IIで示すカイラルスピロ環ホスフィン−窒素−硫黄三座配位子を調製する工程を含むこと、を特徴とする請求項1または請求項3に記載のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子の合成方法。
- 前記式1を有する化合物とグリオキサールジメチルアセタールとルイス酸とメルカプタン(R8SHとR9SH)とのモル比が1:1〜5:0.1〜5:1〜10であり、反応温度が−10〜120oCであること、を特徴とする請求項8に記載の合成方法。
- 前記有機溶媒は、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、テトラヒドロフラン、トルエン、キシレン、メチル−t−ブチルエーテル、ジエチルエーテル、ジオキサン、N,N−ジメチルホルムアミド、ジメチルスルホキシド、ジクロロメタン、クロロホルム、1,2−ジクロロエタンの中の一種または複数種の混合溶媒であり、
前記還元試薬は、水素化アルミニウムリチウム、水素化ホウ素ナトリウム、トリアセトキシ水素化ホウ素ナトリウム、シアノ水素化ホウ素ナトリウムであり、
前記のアルカリは、有機塩基と無機塩基を含み、有機塩基がピリジン、トリエチルアミン、トリブチルアミン、N−メチルモルホリン、N,N−ジエチルイソプロピルアミンであり、無機塩基が水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウムであり、
前記のカルボキシル基を活性化する試薬がエチルクロロホルメート、イソプロピルクロロホルメート、N,N’−ジシクロヘキシルカルボジイミド、カルボニルジイミダゾールであり、
前記のルイス酸が四塩化チタン、三フッ化ホウ素、三塩化インジウム、四塩化ジルコニウム、四塩化テルル、ケイタングステン酸、硫酸銅であること、を特徴とする請求項4、請求項6または請求項8に記載の合成方法。 - β−ケトエステル、β−ケトアミドおよび単純ケトンなどのカルボニル化合物の不斉触媒水素化反応を触媒することへの、請求項1に記載のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子、そのエナンチオマー、ラセミ体、又はその触媒的に許容される塩の応用。
- まず、前記のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子と遷移金属塩から配位化合物を形成し、そして、β−ケトエステル、β−ケトアミドおよび単純ケトンなどのカルボニル化合物の不斉触媒水素化反応を触媒することに用いること、を特徴とする請求項11に記載のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子、そのエナンチオマー、ラセミ体、又はその触媒的に許容される塩の応用。
- 下記の構造の化合物から選ばれたものであること、を特徴とする請求項1に記載のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子、そのエナンチオマー、ラセミ体、又はその触媒的に許容される塩。
- 前記のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子は、下記の構造の化合物から選ばれたものであること、を特徴とする請求項13に記載のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子、そのエナンチオマー、ラセミ体又はその触媒的に許容される塩。
- 有機溶媒と25〜120oCの反応条件で、まずカイラルスピロ環ホスフィン−窒素−硫黄三座配位子をイリジウム触媒前駆体と0.5〜4時間反応させ、そして、0.1〜50atmの水素ガス雰囲気で攪拌しながら0.1〜3時間反応して水素化反応に必要されるカイラル触媒が得られる工程を含み、
前記のカイラルスピロ環アミン基ホスフィン配位子とイリジウム触媒とのモル比が1:1〜2:1であり、
前記のイリジウム触媒前駆体が[Ir(COD)Cl]2(COD=シクロオクタジエン)、[Ir(COD)2]BF4、[Ir(COD)2]PF6、[Ir(COD)2]SbF6または[Ir(COD)2]OTfであること、を特徴とする請求項12に記載のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子、そのエナンチオマー、ラセミ体又はその触媒的に許容される塩から形成された配位化合物の調製方法。 - 溶媒を除去せずに直接に、または、溶媒を除去して貯留可能な固体として調製して、β−ケトエステル、β−ケトアミドおよび単純ケトンなどのカルボニル化合物の不斉触媒水素化反応を触媒することに用いる、請求項12に記載のカイラルスピロ環ホスフィン−窒素−硫黄三座配位子、そのエナンチオマー、ラセミ体またはその触媒的に許容される塩から形成された配位化合物の応用。
- 有機溶媒において、請求項12に調製した配位化合物をカイラル触媒とし、カルボニル化合物とアルカリを添加し、0.1〜100atmの水素ガス雰囲気にて攪拌しながら0.1〜80時間反応してカイラルアルコール類化合物を得ること、を特徴とするカイラルアルコール類化合物の調製方法。
- カルボニル基基質と触媒とのモル比が100:1〜500000:1(すなわち、触媒の使用量が1〜0.0002mol%である)であり、
基質濃度が0.001〜10.0Mであり、
アルカリが水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、ナトリウムエトキシド、カリウムエトキシド、ナトリウム−t−ブトキシド、カリウム−t−ブトキシド、リチウム−t−ブトキシド、トリエチルアミン、トリブチルアミンまたはN−メチルモルホリンであり、
アルカリ濃度が0.005M〜1.0Mであり、
反応温度が0〜80oCであること、を特徴とする請求項17に記載のカイラルアルコール類化合物の調製方法。 - 前記の有機溶媒がメタノール、エタノール、プロパノール、イソプロパノール、ブタノール、テトラヒドロフラン、トルエン、メチル−tert−ブチルエーテル、ジオキサン、N,N−ジメチルホルムアミド、ジメチルスルホキシドの中の一種または複数種の混合溶媒であること、を特徴とする請求項15または請求項17に記載の調製方法。
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