CN1193020A - 酰氨基膦三价膦酸酯化合物 - Google Patents
酰氨基膦三价膦酸酯化合物 Download PDFInfo
- Publication number
- CN1193020A CN1193020A CN98106073A CN98106073A CN1193020A CN 1193020 A CN1193020 A CN 1193020A CN 98106073 A CN98106073 A CN 98106073A CN 98106073 A CN98106073 A CN 98106073A CN 1193020 A CN1193020 A CN 1193020A
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- CN
- China
- Prior art keywords
- phosphino
- phenyl
- represent
- oxygen
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 54
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 21
- 239000010948 rhodium Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 125000000746 allylic group Chemical group 0.000 claims abstract description 4
- 238000006073 displacement reaction Methods 0.000 claims abstract description 4
- 238000006467 substitution reaction Methods 0.000 claims abstract description 3
- -1 3,5-xylyl Chemical group 0.000 claims description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 51
- 239000001301 oxygen Substances 0.000 claims description 51
- 229910052760 oxygen Inorganic materials 0.000 claims description 51
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 claims description 50
- 238000002360 preparation method Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical compound C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 claims description 8
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 claims description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- YUWFEBAXEOLKSG-UHFFFAOYSA-N hexamethylbenzene Chemical compound CC1=C(C)C(C)=C(C)C(C)=C1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- ULNVTMFBEVVUMH-UHFFFAOYSA-N P.[Cl] Chemical compound P.[Cl] ULNVTMFBEVVUMH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical class ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 44
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 39
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000002425 crystallisation Methods 0.000 description 17
- 230000008025 crystallization Effects 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 229940043279 diisopropylamine Drugs 0.000 description 13
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000004679 31P NMR spectroscopy Methods 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 230000002194 synthesizing effect Effects 0.000 description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 6
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000003003 phosphines Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229960003328 benzoyl peroxide Drugs 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000004454 trace mineral analysis Methods 0.000 description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 2
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 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 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 2
- 229940031826 phenolate Drugs 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JKQXZKUSFCKOGQ-JLGXGRJMSA-N (3R,3'R)-beta,beta-carotene-3,3'-diol Chemical compound C([C@H](O)CC=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C[C@@H](O)CC1(C)C JKQXZKUSFCKOGQ-JLGXGRJMSA-N 0.000 description 1
- CSPVUHYZUZZRGF-RNFRBKRXSA-N (4R,6R)-hydroxy-2,2,6-trimethylcyclohexanone Chemical compound C[C@@H]1C[C@@H](O)CC(C)(C)C1=O CSPVUHYZUZZRGF-RNFRBKRXSA-N 0.000 description 1
- YBYCJQQRZPXLHU-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octahydroisoquinoline Chemical compound C1CNCC2=C1CCCC2 YBYCJQQRZPXLHU-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- GOFIUEUUROFVMA-UHFFFAOYSA-N 1-(1h-indol-5-yl)ethanone Chemical compound CC(=O)C1=CC=C2NC=CC2=C1 GOFIUEUUROFVMA-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 208000002874 Acne Vulgaris Diseases 0.000 description 1
- 229930185327 Actinol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KCMZYCFSSYXEQR-UHFFFAOYSA-N CCCC[K] Chemical compound CCCC[K] KCMZYCFSSYXEQR-UHFFFAOYSA-N 0.000 description 1
- IRDQNLLVRXMERV-UHFFFAOYSA-N CCCC[Na] Chemical compound CCCC[Na] IRDQNLLVRXMERV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 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 description 1
- JAQUASYNZVUNQP-USXIJHARSA-N Levorphanol Chemical compound C1C2=CC=C(O)C=C2[C@]23CCN(C)[C@H]1[C@@H]2CCCC3 JAQUASYNZVUNQP-USXIJHARSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- JKQXZKUSFCKOGQ-LQFQNGICSA-N Z-zeaxanthin Natural products C([C@H](O)CC=1C)C(C)(C)C=1C=CC(C)=CC=CC(C)=CC=CC=C(C)C=CC=C(C)C=CC1=C(C)C[C@@H](O)CC1(C)C JKQXZKUSFCKOGQ-LQFQNGICSA-N 0.000 description 1
- QOPRSMDTRDMBNK-RNUUUQFGSA-N Zeaxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCC(O)C1(C)C)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C QOPRSMDTRDMBNK-RNUUUQFGSA-N 0.000 description 1
- WHLQQRGHOPIIMQ-UHFFFAOYSA-N [2-(2-diphenylphosphanyl-6-methylphenyl)-3-methylphenyl]-diphenylphosphane Chemical compound CC=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(C)=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 WHLQQRGHOPIIMQ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
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- JKQXZKUSFCKOGQ-LOFNIBRQSA-N all-trans-Zeaxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C JKQXZKUSFCKOGQ-LOFNIBRQSA-N 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- ZLWLTDZLUVBSRJ-UHFFFAOYSA-K chembl2360149 Chemical compound [Na+].[Na+].[Na+].O=C1C(N=NC=2C=CC(=CC=2)S([O-])(=O)=O)=C(C(=O)[O-])NN1C1=CC=C(S([O-])(=O)=O)C=C1 ZLWLTDZLUVBSRJ-UHFFFAOYSA-K 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
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- 239000004913 cyclooctene Substances 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- MKXZASYAUGDDCJ-NJAFHUGGSA-N dextromethorphan Chemical compound C([C@@H]12)CCC[C@]11CCN(C)[C@H]2CC2=CC=C(OC)C=C21 MKXZASYAUGDDCJ-NJAFHUGGSA-N 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical class C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- MSBPSFSYBUUPMC-UHFFFAOYSA-N furan-2-ylphosphane Chemical class PC1=CC=CO1 MSBPSFSYBUUPMC-UHFFFAOYSA-N 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 229960003406 levorphanol Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- YSWYYGKGAYSAOJ-UHFFFAOYSA-N phosphane Chemical compound P.P YSWYYGKGAYSAOJ-UHFFFAOYSA-N 0.000 description 1
- 125000000061 phosphanyl group Chemical group [H]P([H])* 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- KBPHJBAIARWVSC-XQIHNALSSA-N trans-lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C KBPHJBAIARWVSC-XQIHNALSSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000001775 zeaxanthin Substances 0.000 description 1
- 229940043269 zeaxanthin Drugs 0.000 description 1
- 235000010930 zeaxanthin Nutrition 0.000 description 1
- 150000004799 α-ketoamides Chemical class 0.000 description 1
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Abstract
新的以(R)或(S)形式存在的以下通式的手性酰氨基膦三价膦酸酯化合物,其中R1,R2,R3和R4及*代表手性中心,通过通式R1C(OH)-CONHR2(Ⅲ)与通式R3R4PCl(Ⅳ)二取代的氯膦在溶剂中和碱的存在下反应制备。作为配体本发明酰氨基膦三价膦酸酯化合物与第Ⅷ族过渡金属,特别是与铑,铱,钌和钯及任选其它配体形成配合物,这种配合物也是本发明的目的;它们作为对映体有择反应,特别是不对称氢化,对映体有择氢置换和烯丙位取代反应的催化剂。
Description
R1代表C2-8-烷基,C3-8-环烷基或芳基-C1-4烷基,
R2代表C1-8-烷基,C3-8-环烷基,芳基-C1-4烷基或芳基
R3和R4各自独立地代表C1-8-烷基,C3-8-环烷基,芳基-C1-4烷基,芳基或杂芳基或R3和R4分别与磷原子一起代表9-二苯并磷杂环戊烷基,9-磷杂双环[3.3.1]壬基或9-磷杂双环[4.2.1]壬基及
*代表手性中心。
本发明还涉及制备式I酰氨基膦三价膦酸酯化合物的方法,这些化合物作为配位体与第VIII族金属及任选其它配位体形成的配合物以及这些配合物作为催化剂在对映体有择反应例如不对称氢化,对映体有择氢置换,烯丙位取代等反应中的应用。
本发明的目的是提供新的手性酰氨基膦三价膦酸酯化合物,该化合物可以上述配合物形式用于对映体有择反应,因此得到高旋光产率。本发明目的通过式I新的手性酰氨基膦三价膦酸酯化合物实现。
在本发明范围中,术语“C1-4烷基”,“C1-8烷基”或“C2-8烷基”指具有多达4或8个碳原子的直链或支链烷基,例如甲基,乙基,丙基,异丙基,丁基,异丁基,叔丁基,戊基,异戊基,新戊基,己基,叔己基,庚基,异庚基,辛基或异辛基。
术语“C3-8环烷基”包括环丙基,环丁基,环戊基,环己基,环庚基和环辛基。
术语“芳基”,或“芳基-C1-4-烷基”中的芳基部分指分别为未取代或被单或多取代的苯基或萘基。所述取代基为卤素,C1-8-烷基和C1-8-烷氧基,卤代C1-8-烷基和C1-8-烷氧基,二(C1-8-烷基)氨基,三(C1-4-烷基)甲硅烷基(优选三甲基甲硅烷基)和苯基,其中存在的几个取代基可以相同或不同。对于“芳基-C1-4-烷基”优选指未取代的苄基。
术语“杂芳基”指具有芳香特征的5-或6-员杂环,其中环中具有一个或多个选自氮,氧和硫的杂原子。5-员杂环基的实例是吡咯基,噻吩基和呋喃基,吡啶基是6-员杂环的实例。而且杂环基可以与上述芳基相同的方式被取代和/或可具有稠合的苯环。杂环基优选没有取代基。
术语“卤素”指氟,氯,溴或碘。
术语“C1-8-烷氧基”指具有多达8个碳原子,优选多达4个碳原子的直链或支链烷氧基。其实例是甲氧基,乙氧基,丙氧基,异丙氧基和丁氧基。
术语“卤代C1-8-烷基”或“卤代C1-8-烷氧基”指分别被一个或多个卤原子,特别是氯或氟取代的烷基或烷氧基。实例分别是三氟甲基,三氯甲基和五氟甲基,及氟代甲氧基和氯代甲氧基。
R3和R4优选具有相同含义。
其中一个R1独立地为叔丁基,R2代表甲基及R3和R4分别代表环己基,苯基,3,5-二甲苯基,3,5-二(三氟甲基)苯基,3,5-二(叔丁基)苯基,3,5-二(叔丁基)-4-甲氧基-苯基或2-呋喃基或R3和R4与磷原子一起代表9-二苯并磷杂环戊烷基的式I酰氨基膦三价膦酸酯化合物是优选的。
其中R3和R4代表3,5-二(叔丁基)苯基的式I酰氨基膦三价膦酸酯化合物是特别优选的。
特别优选的式I酰氨基膦三价膦酸酯化合物是:
(S)-或(R)-N-(二苯基膦基(phosphanyl))-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺,
(S)-或(R)-N-(二环己基膦基)-2-[(二环己基膦基)氧]-3,3,N-三甲基丁酰胺,
(S)-或(R)-N-[二-(2-呋喃基)-膦基]-2-[(二-(2-呋喃基)-膦基)氧]-3,3,N-三甲基丁酰胺,
(S)-或(R)-N-(5H-二苯基膦酰基)-2-[(5H-二苯基膦酰基)氧]-3,3,N-三甲基丁酰胺,
(S)-或(R)-N-[二(3,5-二甲基苯基)-膦基]-2-[(二(3,5-二甲基苯基)-膦基)氧]-3,3,N-三甲基丁酰胺,
(S)-或(R)-N-[二(3,5-二(三氟甲基)苯基)-膦基]-2-[(二-(3,5-二(三氟甲基)苯基)-膦基)氧]-3,3,N-三甲基丁酰胺,
(S)-或(R)-N-[二(3,5-二(叔丁基)苯基)-膦基]-2-[(二(3,5-二(叔丁基)苯基)-膦基)氧]-3,3,N-三甲基丁酰胺,和
(S)-或(R)-N-[二(3,5-二(叔丁基)-4-甲氧基苯基)-膦基]-2-[(二(3,5-二(叔丁基)-4-甲氧基苯基)-膦基)氧]-3,3,N-三甲基丁酰胺。
本发明的式I酰氨基膦三价膦酸酯化合物与第VIII族过渡金属,特别是铑,铱,钌和钯形成配合物(符合配位规则),这种配合物也是本发明的目的;它们被用作对映体有择反应,特别是不对称氢化,对映体有择氢置换和烯丙位取代反应的催化剂。
本发明的式I化合物与第VIII族过渡金属形成的配合物可含有其它配位体。这种配合物(也是本发明)的实例具体是下列通式的光学活性的阳离子和中性铑,铱,钌和钯配合物。
[Rh(Y)(L)n]+A- II-a
[Rh(Y)(L)nB] II-b
[Ir(Y)(L)n]+A- II-c
[Ir(Y)(L)nB] II-d
[Ir(Y)(B)4]- rMr+ II-e
[IrH(Y)(B)2] II-f
[Ir(Y)(B)3]2 II-g
[Ir(B)3(Y)] II-h
[Ru(Y)]2+(A-)2 II-i
[Ru(Y)(B)2] II-j
[Ru(Y)(C1)(C2)2-m](C3)mII-k
[Pd(Y)(B)2] II-l
[Pd(Y)2] II-m
[Pd(Y)(L)n]2+(A-)2 II-n其中
L 代表中性配位体,
A- 代表含氧酸或复合酸的阴离子,
B 代表阴离子配位的配位体
C1 代表苯,对-异丙基苯甲烷,二甲苯或六甲基苯,
C2 代表卤素,
C3 代表卤素或A-,
n 代表0,1或2,
m 代表0,1或2,
r 代表1或2,
Mr+代表碱金属或碱土金属离子或选自(C1-8-烷基)4N+,(苯基)N+(C1-8-烷基)3,(苄基)N+(C1-8-烷基)3的四-取代的铵离子(r分别是1,2,或1),及
Y 代表式I的手性酰氨基膦三价膦酸酯化合物。
术语“中性配位体”(L)表示可交换的配位体,特别是烯烃,例如乙烯,丙烯,环辛烯,1,5-己二烯,降冰片二烯或1,5-环辛二烯;芳香烃,如苯,六甲基苯或对异丙基苯甲烷;腈如乙腈或苄腈;或产生配合物的溶剂分子。在氢化中该配位体可被交换。如果多于一种配位体存在(n=2),它们可以相同或不同。
术语“含氧酸或复合酸”(阴离子A-的源)表示下列酸:H2SO4,HClO4,HBrO4,HIO4,HNO3,H3PO4,H3PO3和CF3SO3H或与元素硼,磷,砷,锑或铋配合的卤素配合物。在这两种酸中,HClO4,CF3SO3H,HPF6,HBF4,HB(苯基)4,HB[3,5(CF3)2-C6F3]4,HSbF6和HAsF6是优选的代表。在每种情况下阴离子A-是通过除去氢离子形成的;其实例是ClO4 -,PF6 -和BF4 -。
术语“阴离子配位的配位体”(B)包括例如卤素,羧酸残基,磺酸盐残基,如甲苯磺酸盐或甲磺酸盐,1,3-二酮酸盐,如乙酰基丙酮酸盐,任意取代的苯酚盐,羟基,硝酸盐,亚硝酸盐,氰酸盐,硫氰酸盐,氰化物,烯丙基和2-甲基烯丙基。当苯酚盐被取代时,C1-4-烷基和卤原子是特别优选的取代基,取代是单或多取代。
特别适宜的碱金属离子(M+)或碱土金属离子(M2+)分别是钠或钾离子,钙或镁离子。
术语“四取代的铵离子”(M+)表示由氮原子和四个相同或不同的选自C1-8-烷基,苯基和苄基的取代基组成,例如阴离子(C1-8-烷基)4N+,(苯基)N+(C1-8-烷基)3和(苄基)N+(C1-8-烷基)3。
术语“卤素”(B,C2或C3)包括氟,氯,溴和碘。对于其中B代表卤素的式II-e配合物,卤素可从相应的碱金属,碱土金属或四取代的铵盐衍生。
本发明式I化合物优选的配合物是式II-a至II-k的光学活性的阳离子和中性铑,铱和钌配合物。
其中R1和R2定义如上,与以下通式的二取代的氯膦(phosphane)
R3R4PCl IV
其中R3和R4定义如上,在溶剂中和碱存在下反应。
式III化合物适宜溶解在溶剂中,优选在惰性气氛下,如氮气或氩气下,将碱(第一种)加入,该反应通常在室温下进行。然后小心冷却溶液,适宜地至约-80℃,随后向其中加入第二种碱,接着慢慢加入适当溶解在溶剂中的氯膦。该反应甚至可以在低温下开始。然后将温度逐渐升高至室温,之后分离这样得到的产物(式I化合物)并根据本身已知的方法纯化。
在本发明方法中,适于“第一碱”规则的碱是仲或叔胺,特别是二烷基胺类或三烷基胺类,例如二甲胺,二乙胺,二丙胺,二异丙胺,三甲胺,三乙胺和三丙胺,适于“第二碱”规则的碱是烷基碱金属或芳基碱金属,例如丙基锂,丁基锂,苯基锂,丁基钠和丁基钾,即仲或叔胺(第一碱)与烷基碱金属或芳基碱金属(第二碱)的混合物。二异丙胺和丁基锂是特别优选的碱。
适宜的溶剂是脂肪烃,优选卤代脂肪烃,例如二氯甲烷和氯仿;和脂肪和环状醚,例如乙醚,叔丁基甲基醚和1,2-二甲氧基乙烷,及二噁烷和四氢呋喃;或这些溶剂的混合物。乙醚或四氢呋喃是制备酰氨基膦三价膦酸酯化合物的优选溶剂。
为了分离和纯化产物,通常将混合物蒸发,将剩余物溶解在适宜的溶剂中,特别是低级脂肪醚,例如乙醚,及过滤除去剩余固体成分后,蒸发滤液至干。将这样得到的手性式I化合物进一步通过结晶,特别是从低级脂肪烃如戊烷中结晶进行纯化。
对映异构体纯的(R)-或(S)-式III化合物可以通过相应的α-酮酰胺R1COCONHR2用对映异构体纯的氢化催化剂以本身已知的方法进行不对称氢化制备[H.Takaya等人,“不对称氢化”(AsymmetricHydrogenation),第1-39页,催化不对称合成,Ed.Iwao Ojima,VCHPublishers,Inc.,New York/Weinheim/Cambridge(1993)以及在该文章结尾引用的参考文献]。
我们惊喜地发现式II-a至II-n的配合物(不仅以由本发明配位体Y(式I手性酰氨基膦三价膦酸酯化合物),第VIII族金属和任选其它配位体组成的单个配合物形式存在,而且以单个组分形式存在)可作为对映体有择反应如不对称氢化的催化剂。式II-a至II-n的配合物本身可从这些组分以本身已知的方法制备,参见例如J.A.C.S.93,3089-3091(1971);化学会志(J.Chem.Soc.),化学通讯(Chem.Comm.),1990,869-871;Tetr.:Asymm.7(11),3059-3062(1996);出处同上,6(1),11-14(1995);F.R.Hartley,铂和钯化学(The Chemistry of Platinum and Palladium),Applied SciencePublishers Ltd.,London 1973;化学会志(J.Chem.Soc.),化学通讯(Chem.Comm.),1986,1338-1339;无机化学(Inorg.Chem.)30,125-130(1991);有机金属化合物(Organometallics)12,1406-1415(1993);以及出处同上15,2440-2449(1996)。
本发明式I化合物与第VIII族金属形成的配合物,特别是上述式II-a至II-k配合物适于,例如催化式V化合物至式VI化合物的不对称氢化,其中HX代表选自HBF4,H2SO4,HPF6,HCl,HBr,HI,H3PO4,HSbF6,HClO4和NaH2PO4的无机酸,或选自C1-8-烷基SO3H,苦味酸,甲酸,低级烷基-和芳基羧酸,例如乙酸,丙酸,和苯甲酸,二羧酸,例如草酸,琥珀酸,马来酸和邻苯二甲酸的强有机酸,和*代表手性中心。
要氢化的式V化合物与用作催化剂的式II-a至II-k之一的金属配合物的摩尔比(反应物:催化剂,一般用“S/C”表示)一般在约20至约80000之间,优选约500至30000。氢化通常在温度约0℃-150℃,优选10℃-100℃,压力约1-约200巴(约0.1MPa-20MPa),优选10-80巴(1MPa-8MPa)下进行。
式VI化合物的游离碱是已知的并且是可药用产物,例如镇咳药右美沙芬和镇痛药左啡诺的有价值的中间体。
本发明配合物也适于,例如作式VII化合物至式VIII化合物的不对称氢化的催化剂,其中R5代表C1-8-烷基,C1-8-烷氧基,苯基,苄基或基团N(R6)2,及R6代表氢,C1-8-烷基,苯基或苄基,*代表手性中心。
式II-a阳离子铑配合物是该不对称氢化的优选催化剂。
铑和本发明配体(式I手性酰氨基膦三价膦酸酯化合物)比例为每摩尔配体约0.05至约5摩尔,优选0.5至2摩尔。要氢化的式VII化合物和式II-a配合物中的铑的摩尔比,即反应物:催化剂(S/C)一般约为20至约100000,特别是约500至约50000。用式II-a配合物进行的式VII化合物的对映体有择氢化可在温度约10℃至约120℃,优选约10℃至约60℃之间进行。该氢化通常在约1至约150巴(约0.1至15MPa),优选5至60巴(0.5至6MPa)压力下进行。
式VIII化合物是合成用于治疗和预防皮肤病,例如痤疮和牛皮癣的类视色素的有价值的中间体[参见,例如Pure & Appl.Chem.57,741(1985)以及欧洲专利公开0802 181 A1]。而且,式VIII化合物(通过水解可被转化为phorenol,并且在进一步反应步骤中被转化为光学活性的actinol)是生产3-羟基-胡萝卜素,特别是生产玉米黄素的重要中间体[参见Pure &Appl.Chem.51,535-564(1979)和Helv.Chim.Acta 63,1451-1455(1980)]。
下列实施例用于说明本发明但不以任何方式限制本发明。在实施例中缩写具有以下含义:GC 气相色谱HPLC 高压液相色谱ee 对映异构体过量RT 室温m.p. 熔点HV 高真空Ac 乙酰基OV/p-Di-溶解在非手性相OV(Ohio Valley Chemicals的产品,Me-β-CD Marietta,OH,USA)中的2,6-二甲氧基-3-戊氧基-β-
环糊精COD 1,5-环辛二烯BIPHEMP(6,6’-二甲基联苯-2,2’-二基)双(二苯基膦)
实施例1(R)-2-羟基-3,3,N-三甲基-丁酰胺(式III化合物)的制备
催化剂溶液如下制备:在一个手套箱中(O2含量<1ppm)将385mg(0.5mmol)[Ru(OAc)2((R)-BIPHEMP)]溶解在40ml 0.025摩尔甲醇的盐酸溶液和40ml二氯甲烷中,随后在20℃搅拌1.5小时,然后转移至密闭的催化剂供应容器中。在2l不锈钢高压釜中装入71.6g(0.5mol)2-酮基-3,3,N-三甲基-丁酰胺和310ml甲醇并密封。用氢气置换空气后,允许催化剂溶液从催化剂供应容器中流入略微加压的高压釜中,并在搅拌,60℃和压力60巴(6MPa)下进行氢化。20小时后终止氢化并将反应混合物蒸发。在室温首先从剩余物的250ml二异丙基醚的溶液中分离出1.2g结晶产物,ee=3%,熔点为135-137℃。通过加入275ml环己烷并在冰浴中搅拌混合物3小时分离,得到43.9g(60.5%)的(R)-2-羟基-3,3,N-三甲基丁酰胺;m.p.69-71℃;[α]D 20=-61.0°(c=1,CHCl3),ee=98.7%(通过在OV-61/p-DiMe-β-CD手性柱上GC测定)。
实施例2(S)-2-羟基-3,3,N-三甲基-丁酰胺(式III化合物)的制备
用类似实施例1的方法进行实验。将55.0g(0.384mol)2-酮基-3,3,N-三甲基-丁酰胺的270ml甲醇和30ml二氯甲烷在催化剂(由296mg(0.384mmol)[Ru(OAc)2((S)-BIPHEMP)]和31ml 0.025摩尔甲醇的盐酸溶液制备)存在下进行不对称氢化,结晶后,得到34.4g(62%)的(S)-2-羟基-3,3,N-三甲基丁酰胺;m.p.=60-62℃;[α]D 20=+59.9°(c=1,CHCl3),ee=99.2%。
实施例3(R)-N-(二苯基膦基-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺的制备
在500ml具有氩气气化侧插阀,搅拌棒和橡胶塞的烧瓶中将3.88g(26.7mmol)(R)-2-羟基-3,3,N-三甲基丁酰胺在RT下溶解在无水四氢呋喃中,用注射器加入0.5ml二异丙胺。搅拌30分钟后,将无色溶液冷却至-78℃并在10分钟内用注射器加入28.5ml(53.5mmol)丁基锂。在-78℃搅拌1小时后,在30分钟内滴加11.8g(53.5mmol)氯二苯基膦(phosphane)的30ml四氢呋喃溶液来处理淡黄色悬浮液,在-78℃60分钟后淡黄色澄清溶液逐渐形成。然后除去冷却浴,在RT下蒸发溶剂并在HV下将剩余的泡沫状黄色油状物干燥5小时。加入200ml乙醚后,形成有氯化锂沉淀的无色悬浮液。在Alox(I,碱性,色谱用氧化铝,活性级别I,CAMAG,CH-4123 Muttenz,Switzerland)上用乙醚在保护性气体吸滤器中过滤黄色上清液。在Schlenk管中在HV下完全蒸发合并的滤液并将剩余物在HV下干燥12小时。用液氮在约-180℃固化剩余的黄色油状物并迅速用50ml戊烷处理。超声处理5分钟后形成无色结晶。在约5℃放置24小时后分离上清液,将白色结晶在0℃用戊烷洗涤两次,每次用20ml,总量40ml,并在HV下干燥2小时。产量;8.41g(61%)(R)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺[(R)-tLANOP]为无色结晶,m.p.95-96℃,[α]D 20=+37.5°(c=1,CHCl3),31P-NMR(δ,ppm):52.5(P-N),115.7(P-O)。
实施例4(S)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺的制备
类似实施例3的合成,将由4.47g(30.7mmol)(S)-2-羟基-3,3,N-三甲基-丁酰胺,0.65ml二异丙胺和32.7ml(61.6mmol)丁基锂的四氢呋喃溶液组成的混合物在约-78℃用13.6g(61.6mmol)氯二苯基膦处理。如实施例3所述方法处理,纯化和结晶得到10.6g(20.6mmol,67%)(S)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺[(S)-tLANOP]为无色结晶,m.p.95-96℃,[α]D 20=-37.7°(c=1,CHCl3),纯度:99%(NMR)。31P-NMR(δ,ppm):52.5(P-N),115.7(P-O)。
实施例5(R)-N-[二-(2-呋喃基)-膦基]-2-[(二-(2-呋喃基)膦基)氧]-3,3,N-三甲基丁酰胺的制备
类似实施例3的合成,将由1.78g(12.3mmol)(R)-2-羟基-3,3,N-三甲基-丁酰胺,0.1ml二异丙胺和13.0ml(61.6mmol)丁基锂的四氢呋喃溶液组成的混合物在-78℃用4.93g(24.6mmol)氯-二(2-呋喃基)-膦处理。如实施例3所述方法处理,纯化和结晶得到2.77g(48%)(R)-N-[二-(2-呋喃基)-膦基]-2-[(二-(2-呋喃基)膦基)氧]-3,3,N-三甲基丁酰胺[(R)-(2-呋喃基)-tLANOP]为无色水解敏感性粉末,纯度:≥95%(NMR)。31P-NMR(δ,ppm):0.8(P-N),64.9(P-O)。
实施例6(R)-N-(二环己基膦基)-2-[(二环己基膦基)氧]-3,3,N-三甲基丁酰胺的制备
类似实施例3的合成,将由3.16g(22.3mmol)(R)-2-羟基-3,3,N-三甲基-丁酰胺,0.5ml二异丙胺和27.8ml(44.5mmol)丁基锂的四氢呋喃溶液组成的混合物在-78℃用10.4g(44.5mmol)氯二环己基膦处理。如实施例3所述方法处理,纯化和结晶得到8.20g(69%)(R)-N-(二环己基膦基)-2-[(二环己基膦基)氧]-3,3,N-三甲基丁酰胺[(R)-Cy-tLANOP]为无色固体,纯度:98%(NMR)。31P-NMR(δ,ppm):65.4(P-N),139.3(P-O)。
实施例7(S)-N-(二环己基膦基)-2-[(二环己基膦基)氧]-3,3,N-三甲基丁酰胺的制备
类似实施例3的合成,将由1.69g(11.9mmol)(S)-2-羟基-3,3,N-三甲基-丁酰胺,0.25ml二异丙胺和14.8ml(23.7mmol)丁基锂的四氢呋喃溶液组成的混合物在-78℃用5.52g(23.7mmol)氯二环己基膦处理。如实施例3所述方法处理,纯化和结晶得到4.20g(66%)(S)-N-(二环己基膦基)-2-[(二环己基膦基)氧]-3,3,N-三甲基丁酰胺[(S)-Cy-tLANOP]为无色水解敏感性粉末(用刮勺压碎后),纯度:98%(NMR)。31p-NMR(δ,ppm):65.4(P-N),139.3(P-O)。
实施例8(R)-N-[双(3,5-二甲基苯基)-膦基]-2-[(双(3,5-二甲基苯基)-膦基)氧]-3,3,N-三甲基丁酰胺的制备
类似实施例3的合成,将由0.66g(4.56mmol)(R)-2-羟基-3,3,N-三甲基-丁酰胺,0.05ml二异丙胺和5.70ml(30.3mmol)丁基锂的四氢呋喃溶液组成的混合物在-78℃用6.63g(30.3mmol)氯双(3,5-二甲基苯基)膦处理。如实施例3所述方法处理,纯化和结晶得到2.23g(73%)(R)-N-[双(3,5-二甲基苯基)-膦基]-2-[(双(3,5-二甲基苯基)-膦基)氧]-3,3,N-三甲基丁酰胺[(R)-3,5-Xyl-tLANOP]为无色水解敏感性粉末,纯度:约90-95%(NMR)。31P-NMR(δ,ppm):53.3(P-N),117.7(P-O)。
实施例9(S)-N-[双(3,5-二(三氟甲基)苯基)-膦基]-2-[(双(3,5-二(三氟甲基)苯基)-膦基)氧]-3,3,N-三甲基丁酰胺的制备
类似实施例3的合成,将由0.76g(5.26mmol)(S)-2-羟基-3,3,N-三甲基-丁酰胺,0.05ml二异丙胺和6.56ml(10.5mmol)丁基锂的四氢呋喃溶液组成的混合物在-78℃用6.63g(10.5mmol)氯双(3,5-二(三氟甲基)-苯基)膦处理。如实施例3所述方法处理,纯化和结晶得到3.55g(64%)(S)-N-[双(3,5-二(三氟甲基)苯基)-膦基]-2-[(双(3,5-二(三氟甲基)苯基)-膦基)氧]-3,3,N-三甲基丁酰胺[(S)-3,5-CF3-tLANOP]为淡棕色水解敏感性油状物,纯度:约90%(NMR)。31P-NMR(δ,ppm):50.8(P-N),112.9(P-O)。
实施例10(R)-N-[双(3,5-二(叔丁基)苯基)-膦基]-2-[(双(3,5-二(叔丁基)苯基)-膦基)氧]-3,3,N-三甲基丁酰胺的制备
类似实施例3的合成,将由0.68g(4.74mmol)(R)-2-羟基-3,3,N-三甲基-丁酰胺,0.05ml二异丙胺和5.93ml(9.48mmol)丁基锂的四氢呋喃溶液组成的混合物在-78℃用4.22g(9.48mmol)氯双(3,5-二(叔丁基)-苯基)膦处理。如实施例3所述方法处理,纯化和结晶得到3.78g(83%)(R)-N-[双(3,5-二(叔丁基)苯基)-膦基]-2-[(双(3,5-二(叔丁基)苯基)-膦基)氧]-3,3,N-三甲基丁酰胺[(R)-3,5-tBu-tLANOP]用刮勺压碎后为无色粉末,纯度:约95%(NMR)。31P-NMR(δ,ppm):56.4(P-N),112.4(P-O)。
实施例11(S)-N-[双(3,5-二(叔丁基)苯基)-膦基]-2-[(双(3,5-二(叔丁基)苯基)-膦基)氧]-3,3,N-三甲基丁酰胺的制备
类似实施例3的合成,将由0.93g(6.4mmol)(S)-2-羟基-3,3,N-三甲基-丁酰胺,0.05ml二异丙胺和8.00ml(12.8mmol)丁基锂的四氢呋喃溶液组成的混合物在-78℃用5.99g(12.8mmol)氯双(3,5-二(叔丁基)-苯基)膦处理。如实施例3所述方法处理,纯化和结晶得到3.41g(3.54mmol,55%)(S)-N-[双(3,5-二(叔丁基)苯基)-膦基]-2-[(双(3,5-二(叔丁基)苯基)-膦基)氧]-3,3,N-三甲基丁酰胺[(S)-3,5-tBu-tLANOP]为无色粉末。纯度:约97%(NMR)。31P-NMR(δ,ppm):56.4(P-N),112.4(P-O)。
实施例12(S)-N-[双(3,5-二(叔丁基)4-甲氧基苯基)-膦基]-2-[(双(3,5-二(叔丁基)4-甲氧基苯基)-膦基)氧]-3,3,N-三甲基丁酰胺的制备
类似实施例3的合成,将由0.59g(4.07mmol)(S)-2-羟基-3,3,N-三甲基-丁酰胺,0.05ml二异丙胺和5.08ml(8.14mmol)丁基锂的四氢呋喃溶液组成的混合物在-78℃用4.11g(8.14mmol)氯双(3,5-二(叔丁基)-4-甲氧基苯基)膦处理。如实施例3所述方法处理,纯化和结晶得到2.63g(60%)(S)-N-[双(3,5-二(叔丁基)4-甲氧基苯基)-膦基]-2-[(双(3,5-二(叔丁基)4-甲氧基苯基)-膦基)氧]-3,3,N-三甲基丁酰胺[(S)-3,5-tBu,4-MeO-tLANOP]为无色氧化敏感性粉末。纯度:约95%(NMR)。31P-NMR(δ,ppm):54.2(P-N),110.8(P-O)。
实施例13(S)-N-(5H-二苯并磷杂环戊烷基)-2-[(5H-二苯并磷杂环戊烷基)氧]-3,3,N-三甲基丁酰胺的制备
类似实施例3的合成,将由2.20g(15.2mmol)(S)-2-羟基-3,3,N-三甲基-丁酰胺,0.3ml二异丙胺和19.0ml(30.3mmol)丁基锂的四氢呋喃溶液组成的混合物在-78℃用6.63g(30.3mmol)5-氯-5H-二苯膦酯(dibenzophosphol)处理。如实施例3所述方法处理,纯化和结晶得到4.74g(62%)(S)-N-(5H-二苯并磷杂环戊烷基)-2-[(5H-二苯并磷杂环戊烷基)氧]-3,3,N-三甲基丁酰胺[(S)-Diphol-tLANOP]为无色粉末。纯度:≥90%(NMR)。31P-NMR(δ,ppm):40.4(P-N),112.2(P-O)。
实施例14[(R)-2-(1-二甲氨基-乙基)-苯基-C,N]-[(S)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺]-Pd(II)四氟硼酸盐的制备
该配合物适于所提到的式I化合物的表征。
称取105mg(0.250mmol)双-(乙腈)-[(R)-2-(1-二甲氨基-乙基)-苯基]-Pd-(II)四氟硼酸盐和129mg(0.250mmol)(S)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺置于在手套箱中的50ml具有搅拌棒和橡胶塞的Schelenk管中并溶解在10ml二氯甲烷中。在RT下搅拌10分钟后,在RT和HV下蒸发无色澄清溶液至干。用10ml乙醚洗涤无色剩余物并在HV下干燥2小时。产量:211mg(98%)[(R)-2-(1-二甲氨基-乙基)-苯基-C,N]-[(S)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺]-Pd(II)四氟硼酸盐。纯度:约98%(.NMR)。微量分析:
C H N计算值 57.60 5.54 3.28实测值 57.42 5.54 3.08
实施例15[(环辛-1,5-二烯)-[(R)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺]-Rh(I)四氟硼酸盐的制备
在搅拌,RT下和2分钟内,将189mg(0.368mmol)(R)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺的10ml四氢呋喃溶液滴加到100ml Schlenk管中的144mg(0.355mmol)双-(环辛-1,5-二烯)-Rh(I)四氟硼酸盐的四氢呋喃悬浮液中。这时橙-棕色悬浮液立即变成澄清的黄-橙色溶液,搅拌15分钟后,在HV和室温下蒸发。在HV下干燥2小时后,将剩余的橙色油状物悬浮在10ml乙醚中,在RT下放置12小时后分离上清液并将黄色精细结晶固体在HV下干燥12小时。产量:278mg(97%)[(环辛-1,5-二烯)-[(R)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺]-Rh(I)四氟硼酸盐。纯度:≥99%(NMR)。微量分析:
C H N P计算值 57.73 5.59 1.73 7.63实测值 57.51 5.59 1.46 7.41
实施例16[(环辛-1,5-二烯)-[(S)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺]-Ir(I)四氟硼酸盐的制备
类似实施例15所述合成,将由96mg(0.195mmol)双-(环辛-1,5-二烯)-Ir(I)四氟硼酸盐和100mg(0.195mmol)(S)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺的20ml四氢呋喃溶液组成的混合物在RT下搅拌30分钟。如实施例15所述方法处理和结晶得到139mg(80%)[(环辛-1,5-二烯)-[(S)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺]-Ir(I)四氟硼酸盐为红色晶体。纯度:≥99%(NMR)。微量分析:
C H N P计算值 52.00 5.04 1.56 6.88实测值 51.93 4.95 1.51 6.43
实施例171-(4-甲氧基苄基)-3,4,5,6,7,8-六氢异喹啉四氟硼酸盐的催化氢化
将13.4mg(0.020mmol)[IrCl(COD)]2和作为手性配体的57.7mg(0.060mmol)(R)-3,5-tBu-tLANOP溶解在手套箱(O2含量<1ppm)中的35ml具有玻璃附件的高压釜中的4ml甲苯中。加入59.1mg(0.16mmol)四丁基碘化铵(Bu4N+I-)并搅拌30分钟后,将0.343g(1.0mmol)1-(4-甲氧基-苄基)-3,4,5,6,7,8-六氢异喹啉四氟硼酸盐和4ml甲醇加到该催化剂溶液中。然后将高压釜密封并在搅拌,25℃和氢气压力100巴(10MPa)下氢化44小时。在40℃/20毫巴(2kPa)的旋转蒸发器上蒸发黄色氢化溶液。根据HPLC[柱:ChiralP AK AD(Daicel Chem.Ind.Ltd.;catalogue No.7407-00),洗脱剂:10%乙醇和0.2%三乙胺的己烷]和GC[(-)-樟脑酸酰胺,柱:OV-240OH(OhioValley Chemicals,Marietta,OH,USA;catalogue No.091785)15m]分析,完全转化的剩余物含有48%(S)-1-(4-甲氧基苄基)-1,2,3,4,5,6,7,8-八氢异喹啉,其中ee为72%。
实施例17.1-17.7
用表1中所列手性配体以类似实施例17的方式氢化1-(4-甲氧基苄基)-3,4,5,6,7,8-六氢异喹啉HX盐。用HX=HBF4和HPF6的实验在甲苯(4ml)/甲醇(4ml)中进行,用HX=H2SO4的实验在四氢呋喃(8ml)/水(0.2ml)中进行。
表1
a)加入0.026mnolBiI3代替Bu4N+I-;b)加入0.08mmol邻苯二甲酰亚胺代替Bu4N+I-;c)温度=80℃,S/C:5000;
实施例号 | HX | 手性配体 | %选择性 | %ee |
17.1a17.2b17.317.417.5a17.6c17.7 | HBF4HBF4HBF4H2SO4H2SO4H2SO4HPF6 | (R)-3,5-tBu-tLANOP″(S)-3,5-tBu,4-MeO-tLANOP(S)-3,5-tBu-tLANOP(R)-3,5-tBu-tLANOP(R)-3,5-tBu-tLANOP(S)-3,5-tBu,4-MeO-tLANOP | 55805546366652 | 67(R)65(R)78(S)86(S)73(R)70(R)78(S) |
实施例18.1和18.24-乙酰氧基-2,6,6-三甲基环己-2,4-二烯-1-酮的催化氢化
用表2所列手性配体以类似实施例17的方式将4-乙酰氧基-2,6,6-三甲基环己-2,4-二烯-1-酮氢化为4-乙酰氧基-2,6,6-三甲基环己-2-烯-1-酮。
表2a)Rh(BF4):由[Rh(COD)2]BF4和手性配体现场制备的配合物;条件:S/Rh100,乙酸乙酯,RT,10巴(1Mpa)氢气。
Claims (13)
2.根据权利要求1的酰氨基膦三价膦酸酯化合物,其中R3和R4具有相同含义。
3.根据权利要求1或2的酰氨基膦三价膦酸酯化合物,其中R1代表叔丁基。
4.根据权利要求1-3之一的酰氨基膦三价膦酸酯化合物,其中R2代表甲基。
5.根据权利要求1-4之一的酰氨基膦三价膦酸酯化合物,其中R3和R4各自独立地代表环己基,苯基,3,5-二甲苯基,3,5-二(三氟甲基)苯基,3,5-二(叔丁基)苯基,3,5-二(叔丁基)-4-甲氧基苯基或2-呋喃基或R3和R4与磷原子一起代表9-二苯并磷杂环戊烷基。
6.根据权利要求1的酰氨基膦三价膦酸酯化合物,其选自
(R)-或(S)-N-(二苯基膦基)-2-[(二苯基膦基)氧]-3,3,N-三甲基丁酰胺,
(R)-或(S)-N-[二-(2-呋喃基)-膦基]-2-[(二-(2-呋喃基)-膦基)氧]-3,3,N-三甲基丁酰胺,
(R)-或(S)-N-(二环己基膦基)-2-[(二环己基膦基)氧]-3,3,N-三甲基丁酰胺,
(R)-或(S)-N-[二(3,5-二甲基苯基)-膦基]-2-[(二(3,5-二甲基苯基)-膦基)氧]-3,3,N-三甲基丁酰胺,
(R)-或(S)-N-[二(3,5-二(叔丁基)苯基)-膦基]-2-[(二(3,5-二(叔丁基)苯基)-膦基)氧]-3,3,N-三甲基丁酰胺,和
(R)-或(S)-N-[二(3,5-二(叔丁基)-4-甲氧基苯基)-膦基]-2-[(二(3,5-二(叔丁基)-4-甲氧基苯基)-膦基)氧]-3,3,N-三甲基丁酰胺,
(R)-或(S)-N-(5H-二苯基膦酰基)-2-[(5H-二苯基膦酰基)氧]-3,3,N-三甲基丁酰胺和
(R)-或(S)-N-[二(3,5-二(三氟甲基)苯基)-膦基]-2-[(二-(3,5-二(三氟甲基)苯基)-膦基)氧]-3,3,N-三甲基丁酰胺。
7.权利要求1的式I酰氨基膦三价膦酸酯化合物与第VIII族金属形成的配合物。
8.根据权利要求7的配合物,其中第VIII族金属是钌,铑,铱或钯。
9.权利要求7或8的配合物,其中不仅含有作为配体的式I酰氨基膦三价膦酸酯化合物,还含有一种或多种其它配体,特别是下列通式的光学活性的阳离子和中性铑,铱,钌和钯配合物
[Rh(Y)(L)n]+A- II-a
[Rh(Y)(L)nB] II-b
[Ir(Y)(L)n]+A- II-c
[Ir(Y)(L)nB] II-d
[Ir(Y)(B)4]r -Mr+ II-e
[IrH(Y)(B)2] II-f
[Ir(Y)(B)3]2 II-g
[Ir(B)3(Y)] II-h
[Ru(Y)]2+(A-)2 II-i
[Ru(Y)(B)2] II-j
[Ru(Y)(C1)(C2)2-m](C3)m II-k
[Pd(Y)(B)2] II-l
[Pd(Y)2] II-m
[Pd(Y)(L)n]2+(A-)2 II-n其中
L 代表中性配位体,
A- 代表含氧酸或复合酸的阴离子,
B 代表阴离子配位的配位体
C1 代表苯,对-异丙基苯甲烷,二甲苯或六甲基苯,
C2 代表卤素,
C3 代表卤素或A-,
n 代表0,1或2,
m 代表0,1或2,
r 代表1或2,
Mr+代表碱金属或碱土金属离子或选自(C1-8-烷基)4N+,(苯基)N+(C1-8-烷基)3,(苄基)N+(C1-8-烷基)3的四-取代的铵离子(r分别是1,2或1),及
Y 代表式I的手性酰氨基膦三价膦酸酯化合物。
10.权利要求9的式II-a至II-k的配合物。
12.根据权利要求1的方法,其中卤代脂肪烃,脂肪或环状醚或这些溶剂的混合物用作溶剂,仲胺或叔胺与烷基碱金属或芳基碱金属的混合物用作碱。
13.权利要求7-10之一的配合物作为对映体有择反应,特别是不对称氢化,对映体有择氢置换和烯丙位取代反应的催化剂的用途。
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EP97103963 | 1997-03-10 | ||
EP97103963.1 | 1998-01-23 | ||
EP98101128 | 1998-01-23 | ||
EP98101128.1 | 1998-01-23 |
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CN1193020A true CN1193020A (zh) | 1998-09-16 |
CN1098856C CN1098856C (zh) | 2003-01-15 |
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US (1) | US6348612B1 (zh) |
EP (1) | EP0864576A1 (zh) |
JP (1) | JPH10251281A (zh) |
KR (1) | KR19980080036A (zh) |
CN (1) | CN1098856C (zh) |
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CA (1) | CA2230770C (zh) |
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US6806391B2 (en) | 2002-07-31 | 2004-10-19 | Shell Oil Company | Process for the carbonylation of ethylenically unsaturated compounds and bidentate diphosphine composition used in this process |
US7084089B2 (en) | 2002-07-31 | 2006-08-01 | Shell Oil Company | Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and a process for preparation of this bidentate diphosphine composition |
US7013601B2 (en) * | 2004-07-22 | 2006-03-21 | Coastal Planters, Llc | Plant container with hanger |
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1998
- 1998-03-02 CA CA002230770A patent/CA2230770C/en not_active Expired - Lifetime
- 1998-03-02 EP EP98103615A patent/EP0864576A1/de not_active Withdrawn
- 1998-03-05 US US09/035,554 patent/US6348612B1/en not_active Expired - Lifetime
- 1998-03-09 KR KR1019980007714A patent/KR19980080036A/ko not_active Application Discontinuation
- 1998-03-09 CN CN98106073A patent/CN1098856C/zh not_active Expired - Lifetime
- 1998-03-10 JP JP10057602A patent/JPH10251281A/ja active Pending
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CN1098856C (zh) | 2003-01-15 |
BR9800862A (pt) | 2000-03-21 |
CA2230770A1 (en) | 1998-09-10 |
KR19980080036A (ko) | 1998-11-25 |
US6348612B1 (en) | 2002-02-19 |
EP0864576A1 (de) | 1998-09-16 |
CA2230770C (en) | 2007-02-20 |
JPH10251281A (ja) | 1998-09-22 |
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