WO2002040492A1 - Diphosphines chirales et leurs complexes metalliques - Google Patents
Diphosphines chirales et leurs complexes metalliques Download PDFInfo
- Publication number
- WO2002040492A1 WO2002040492A1 PCT/FR2001/003607 FR0103607W WO0240492A1 WO 2002040492 A1 WO2002040492 A1 WO 2002040492A1 FR 0103607 W FR0103607 W FR 0103607W WO 0240492 A1 WO0240492 A1 WO 0240492A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- group
- alkyl
- compound
- diphosphino
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims description 7
- 239000002184 metal Substances 0.000 title claims description 7
- 150000001875 compounds Chemical group 0.000 claims abstract description 67
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 48
- -1 methylene dioxy Chemical group 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 125000003545 alkoxy group Chemical group 0.000 claims description 23
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 150000002367 halogens Chemical class 0.000 claims description 20
- 125000003118 aryl group Chemical group 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
- 238000006243 chemical reaction Methods 0.000 claims description 15
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 10
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 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 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 125000006272 (C3-C7) cycloalkyl group Chemical group 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 238000006366 phosphorylation reaction Methods 0.000 claims description 3
- 238000005694 sulfonylation reaction Methods 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 claims description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- GRTJBNJOHNTQBO-UHFFFAOYSA-N [2-(2-diphenylphosphanylphenyl)phenyl]-diphenylphosphane Chemical group C1=CC=CC=C1P(C=1C(=CC=CC=1)C=1C(=CC=CC=1)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 GRTJBNJOHNTQBO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000005530 alkylenedioxy group Chemical group 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 2
- 150000004718 beta keto acids Chemical class 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000004721 gamma keto acids Chemical class 0.000 claims description 2
- 125000005283 haloketone group Chemical group 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims 1
- HAUFGPBAHXHBCM-UHFFFAOYSA-N 4-diphenylphosphanyl-5-(2-diphenylphosphanyl-6-methoxyphenyl)bicyclo[4.1.0]hepta-1(6),4-diene-2,3-dione Chemical group COC1=CC=CC(=C1C1=C(C(C(C2=C1C2)=O)=O)P(C1=CC=CC=C1)C1=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 HAUFGPBAHXHBCM-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000000213 sulfino group Chemical group [H]OS(*)=O 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- 239000012429 reaction media Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 241001631457 Cannula Species 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 0 Cc(c(C)c1-c2c(*)c(C)c(*)cc2O)c(*)cc1O Chemical compound Cc(c(C)c1-c2c(*)c(C)c(*)cc2O)c(*)cc1O 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000019502 Orange oil Nutrition 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000010502 orange oil Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- DVENPLHJIDSVCG-UHFFFAOYSA-N 2-iodonaphthalen-1-ol Chemical compound C1=CC=C2C(O)=C(I)C=CC2=C1 DVENPLHJIDSVCG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 2
- BNJXHRMYHDWZKL-UHFFFAOYSA-N 2-iodobenzene-1,3-diol Chemical compound OC1=CC=CC(O)=C1I BNJXHRMYHDWZKL-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- KHOITXIGCFIULA-UHFFFAOYSA-N Alophen Chemical compound C1=CC(OC(=O)C)=CC=C1C(C=1N=CC=CC=1)C1=CC=C(OC(C)=O)C=C1 KHOITXIGCFIULA-UHFFFAOYSA-N 0.000 description 2
- XLSGIJCMIPKKNO-UHFFFAOYSA-N IC1(CC=CC2=CC=CC=C12)OC(CC(C)O)C Chemical compound IC1(CC=CC2=CC=CC=C12)OC(CC(C)O)C XLSGIJCMIPKKNO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 1
- GTCCGKPBSJZVRZ-RFZPGFLSSA-N (2r,4r)-pentane-2,4-diol Chemical compound C[C@@H](O)C[C@@H](C)O GTCCGKPBSJZVRZ-RFZPGFLSSA-N 0.000 description 1
- GTCCGKPBSJZVRZ-WHFBIAKZSA-N (2s,4s)-pentane-2,4-diol Chemical compound C[C@H](O)C[C@H](C)O GTCCGKPBSJZVRZ-WHFBIAKZSA-N 0.000 description 1
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 description 1
- 125000006704 (C5-C6) cycloalkyl group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZEQODERAFRLPPW-UHFFFAOYSA-N 2-bromo-3,4,5-trimethylphenol Chemical compound CC1=CC(O)=C(Br)C(C)=C1C ZEQODERAFRLPPW-UHFFFAOYSA-N 0.000 description 1
- DLVPKRMLAXQBGK-UHFFFAOYSA-N 2-iodo-3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1I DLVPKRMLAXQBGK-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- LYNZPOSJCHNPML-UHFFFAOYSA-N 3-diphenylphosphanyl-4-(3-diphenylphosphanyl-2-bicyclo[4.1.0]hepta-1(6),2,4-trienyl)-5-methoxycyclohexa-3,5-diene-1,2-dione Chemical group COC1=CC(C(C(=C1C1=C(C=CC2=C1C2)P(C1=CC=CC=C1)C1=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1)=O)=O LYNZPOSJCHNPML-UHFFFAOYSA-N 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- LDYFSVJKRCYQDG-MNOVXSKESA-N IC1=C(C=CC2=CC=CC=C12)O[C@H](C[C@@H](C)O)C Chemical compound IC1=C(C=CC2=CC=CC=C12)O[C@H](C[C@@H](C)O)C LDYFSVJKRCYQDG-MNOVXSKESA-N 0.000 description 1
- DJEPNZQCBIVNBJ-UHFFFAOYSA-N IC1C(O)=CC=CC1(O)OC Chemical compound IC1C(O)=CC=CC1(O)OC DJEPNZQCBIVNBJ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- FNCQSSIMHQVKGF-UHFFFAOYSA-N diphenyl-(2-phenylphenyl)phosphane Chemical group C1=CC=CC=C1P(C=1C(=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 FNCQSSIMHQVKGF-UHFFFAOYSA-N 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical group O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
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- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0033—Iridium compounds
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0073—Rhodium compounds
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
- C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
- B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
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- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
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- B01J2531/82—Metals of the platinum group
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- C07B2200/07—Optical isomers
Definitions
- the present invention relates to asymmetric atropoisomeric diphosphines, their synthesis and their uses as optically active ligands for the preparation of diphosphino-metal complexes.
- the invention also relates to diphosphino-metallic complexes comprising an asymmetric chiral diphosphine as a ligand and the asymmetric catalysis processes using these complexes.
- the invention more particularly contemplates the use of these diphosphino-metallic complexes in hydrogenation or asymmetric hydrogen transfer processes for the synthesis of organic products with desired chirality.
- a dissymmetrical atropoisomeric ligand, FUPMOP is known in the prior art, used for the synthesis of diphosphino-metallic complexes, having enantioselective catalytic properties in hydrogenation (M. Murata et al. Synlett, 1991, page 827).
- the applicant has now designed new diphosphino-metallic complexes, comprising an asymmetric atropoisomer diphosphine as optically active ligand, very particularly useful for the synthesis of organic products, with desired chirality with very high yields and enantioselectivity.
- the subject of the invention is therefore a chiral diphosphine (R) or (S) of general formula (I):
- R 5 and R 6 are chosen from a hydrogen atom, a halogen such as chlorine, bromine or fluorine, a C 1 alkyl group saturated or not, a C 1 alkoxy group -4 saturated or unsaturated, a C 4 _ 6 aryloxy group, said alkyl, alkoxy or aryloxy groups being optionally substituted by a halogen, a hydroxy, a C 1 alkyl or a benzyl,
- R 2 and R 3 or R 4 and R 5 together form a benzene ring, optionally substituted, a methylene dioxy, ethylene dioxy, C 3 _ 7 cycloalkyl group, saturated or not, such as an optionally substituted cyclohexyl, or another heterocyle of formula (II):
- W and Q are chosen from an oxygen atom, a function sulfoxide (-SO), sulfone (-S0 2 ) or a methylene group, and n is 0 or 1,
- R 3 and R 4 form a ring such as a C 2 _ 4 alkylene dioxy such as a methylene dioxy, an ethylene dioxy, a C 3 _ 7 cycloalkyl saturated or not, such as an optionally substituted cyclohexyl, a heterocyle of formula (II) optionally substituted by a halogen, a hydroxy, a C t _ 5 alkyl or a C- ⁇ alkoxy;
- R 7 and R 8 identical or different, represent an aryl optionally substituted by an alkyl, a halogen or an alkoxy such as for example a phenyl, a tolyl, a trimethylphenyl or a tert-butylphenyl, or represents a C 5 _ 6 cycloalkyl, such as for example a cyclopentyl, a cyclohexyl, optionally substituted by an alkyl, a halogen or an alkoxy.
- the invention excludes the compounds of formula (I) in which R 3 and / or R 4 represent a hydrogen atom, R x has the same meaning as R 6 , R 2 has the same meaning as R 5 and R 3 a the same meaning as R 4 .
- the chiral diphosphines (R) or (S) of formula (I) of the present invention are prepared by a method of the type described by D. CAI et al. (J. Org. Chem. 1994, p 7180), from the compounds of formulas (XIII) then (XII) according to the reaction scheme shown in Figure 1 of the accompanying drawings.
- triflic anhydride trifluoromethanesulfonic anhydride
- R ⁇ r R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 have the same meanings as in formula (I).
- R x to R 6 have the same meaning as in formula (I) above and R and R ′, which are identical, represent either a group —OH or a group of formula —P (R 7 ) (R 8 ) where R 7 and R 8 have the same meaning as in formula (I).
- a diphosphine of atropoisomeric chirality (R) or (S), asymmetrical thanks to the difference of the cycles A and B of general formula (I) according to the invention is remarkable as an optically active ligand for the preparation of diphosphino-metal complexes.
- the mixed atropoisomeric diphosphines of formulas (I) are used according to the invention for the preparation of several types of diphosphino-metallic complexes active in asymmetric catalysis in the hydrogenation processes.
- a first group of diphosphino-metallic complexes prepared, using the chiral diphosphines of formula (I) according to the invention, corresponds to the following formula (III):
- - M represents a metal such as ruthenium, rhodium or iridium
- - X represents a halogen such as chlorine, bromine, fluorine or iodine
- Sv represents a tertiary amine, a ketone, an ether
- - L represents a chiral diphosphine (R) or (S), of formula (I) above;
- - y is an integer equal to 0 or 1;
- - x is an integer equal to 1 or 2;
- - z is an integer equal to l, 2, or 4;
- diphosphino-metallic complexes of formulas (III) the invention envisages more particularly the complexes of formulas (IIIA) and (IIIB).
- Ar represents an olefin such as ethylene, 1,3-butadiene, cyclohexadiene, norbonadiene, cycloocta-1,5-diene, a pi-all le, a nitrile such as acetonitrile, an arene of formula (V):
- R 9 , R 10 , R llf R 12 , R 13 and R 14 identical or different, are chosen from a hydrogen atom, a C x _ 5 alkyl group, an isoalkyl group, a tertioalkyl group, an alkoxy group , said groups possibly comprising one or more heteroatoms such as 0, N and Si,
- - Y represents an anion, such as C10 4 " , BF 4 ⁇ , PF 6 " , and - j is an integer equal to 0 or 1, m is an integer equal to 1, 2 or 4 and n is an integer equal to 1 or 2.
- a third group of diphosphino-metallic complexes prepared using the chiral diphosphines of formula (I) of the invention corresponds to the following formula (VI):
- M, X and L have the same meaning as in formula (III), and R 15 and R 16 , identical or different, represent a phenyl or a phenyl substituted by an alkyl, an alkoxy or a dialkylamino.
- a fourth group of diphosphino-metallic complexes prepared using the chiral diphosphines of formula (I) according to the invention corresponds to the following formula (VII): M (L) Z 2 (VII) in which: M and L have the same meaning as in formula (III) and Z represents an acetate group of formula R 17 COO " , diacetate of formula " OOCR 17 COO " , an amino acetate of formula R 17 CH (NH 2 ) COO ⁇ , where R 17 represents a C 1-4 alkyl, a C 1-4 haloalkyl, a substituted or unsubstituted phenyl.
- a fifth group of diphosphino-metallic complexes prepared using the chiral diphosphines of formula (I) according to the invention corresponds to the following formula (VIII):
- - W represents zinc, aluminum, titanium or tin; - ' represented :
- a sixth group of diphosphino-metallic complexes prepared using the chiral diphosphines of formula (I) according to the invention corresponds to the following formula (IX): MH (L) 2 Y (IX) in which: M and L have the same meaning as in formula (III), H represents a hydrogen atom and Y represents an anion, such as C10 4 " ,
- a seventh group of diphosphino-metallic complexes prepared using the chiral diphosphines of formula (I) according to the invention corresponds to the following formula (X): M (L) Y 2 (X) in which: M and L have the same meaning as in formula (III) and Y represents an anion, such as C10 4 " , BF 4 ⁇ , PF 6 " .
- An eighth group of diphosphino-metallic complexes prepared using the chiral diphosphines of formula (I) according to the invention corresponds to the following formula (XI):
- M and L have the same meaning as in formula (III) and Y represents an anion, such as C10 4 ⁇ , BF 4 " , PF 6 " .
- the chiral diphosphines (R) or (S) of formula (I) of the present invention are prepared by a method of the type described by D. CAI et al. (J. Org. Chem. 1994, p 7180), starting from the compounds of formulas (XIII) then (XII) according to the reaction scheme represented in FIG. 1 of the attached drawings.
- triflic anhydride trifluoromethanesulfonic anhydride
- R x to R 6 have the same meanings as in formula (I).
- the compound of formula (XIII) is prepared from the compounds of formulas (XV) and (XIV) according to the reaction scheme shown in Figure 2 of the accompanying drawings.
- R 1f R 2 , R 3 , R 4 , R 5 and R 6 have the same meanings as in formula (I)
- R 19 represents an alkyl such as methyl, ethyl or an aryl such as phenyl
- X ' represents a bromine or iodine atom
- n' represents an integer equal to 0, 1, 2, 3 or 4.
- the compound of formula (XV) is obtained by a Mitsunobu type reaction between the compounds of formula (XVI) and (XVII) below:
- R19 and X have the same meaning as in formulas (XV) and (XIV) and R 17 represents an alkyl, aryl or arylalkyl group such as methyl, ethyl, phenyl or benzyl.
- R lf R 2 , R 3 , R 4 , R 5 and R 6 have the same meanings as in formula (I) and X 'represents a bromine or iodine atom .
- R x to R 6 have the same meanings as above.
- the compounds of formulas (VI) can be prepared from compounds of formula (XXII): [MX (P (R 15 ) 2 (R 16 )) (DMA)] 2 X (XXII) in which M, X, R 15 and R 16 have the same meanings as in formula (VI) and DMA represents dimethylacetamide .
- the complexes of formulas (VII), (VIII), (IX), (X) and (XI) can also be prepared by analogy according to methods described in the prior art.
- the complexes of formulas (VII) and (VIII) can be obtained from the compounds of formulas (IIIA) by analogy to the methods described in the European patent applications published under No. 245 960 and 271 310.
- the complexes of formulas (IX), (X) and (XI) can be obtained from the compounds of formula (IIIB) by analogy to the methods described in the European patent applications published under Nos. 256 634, 245 959 and 271 310.
- the present invention also relates to the diphosphino-metallic complexes of formulas (III), (IV), (VI), (VII), (VIII), (IX), (X) and (XI), as well as their use as catalyst in asymmetric catalysis processes and more particularly, their use in asymmetric hydrogenation or hydrogen transfer processes, of unsaturated compounds carrying functional groups of formula (XXIII) below:
- a and B are different and chosen from a C ⁇ alkyl group, an aryl group, a C 1-7 hydroxyc arbonyl group, a C x 7 alkoxycarbonyl group, an aryloxycarbonyl group in C ⁇ i o , a halogenoalkyl group C ⁇ _ ⁇ , a heteroaryl group, a cycloalkyl group saturated or not, said alkyl groups, aryl, cycloalkyl optionally comprising one or more substituents chosen from a halogen such as chlorine, fluorine, bromine, an N0 2 group, a C ⁇ alkyl, a C- ⁇ alkoxy, a C 1-7 cycloalkyl, fused or not, an aryl group, fused or not, optionally substituted by a halogen, a C ⁇ alkyl , a C ⁇ alkoxy, said alkyl, cycloalkyl or aryl groups
- - Q- L represents an oxygen, a group -NR 21 , -NOR 21 or -C (R 21 ) 2 , where R 21 is chosen from a C 1 _ 5 alkyl, an aryl group, a heteroaryl group substituted by a C ⁇ alkyl.
- non-limiting examples that may be mentioned: ene-acid or ester derivatives, en-alcohol or ether derivatives, en-amide derivatives, derivatives enamine, beta-keto acid or ester derivatives, gamma-keto acid or ester derivatives, beta, gamma-dicetoacid derivatives or ester, halo-ketone derivatives, hydroxy or alkoxy-ketone derivatives, imine derivatives.
- a preferred asymmetric hydrogenation process comprises the treatment of a compound of formula (XXIII), in an appropriate solvent, in the presence of a catalytic complex of formulas (III), (IV), (VI), (VII), (VIII), (IX), (X) or (XI), as a catalyst, under the operating conditions preferably as follows: - a temperature between 0 and + 150 ° C,
- An amount of catalyst relative to the amount of substrate between 1/50000 and 1/10, preferably between 1/10000 and 1/10, most preferably 1/10000 and 1/1000.
- the hydrogenation time will generally be greater than or equal to one hour. Depending on the substrate and the catalyst, it may, for example, be between 1 hour and 70 hours. Any solvent can be used, isolated or mixed, as long as it can dissolve the substrate and does not affect the reaction. Among the solvents which may be used in the above process, mention may be made of water, a hydrocarbon such as hexane, heptane, octane, nonane, decane, le.
- benzene, toluene and xylene an ether such as tetrahydrofuran, dioxane, dimethoxyethane, diisopropyl ether and diethylene glycol dimethyl ether, an ester such as ethyl acetate, butyl acetate and propionate ethyl, a ketone such as acetone, diisopropylcone tone, methylisobutyl ketone, methyl ethyl ketone and acetylacetone, an amide such as dimethylformamide, an alcohol such as methanol, ethanol, n-propanol and isopropanol, a nitrile like acetonitrile, a o
- alkyl halide such as dichloromethane, chloroform and 1,2-dichlroethane, an a such as triethylamine, diisobutylamine, triethylamine, N-methylpiperidine, ethyldiisopropylamine, N-methylcyclohexylamine and pyridine, an acid organic like acetic acid, propionic acid and formic acid.
- the solution is treated with 250ml of 10% hydrochloric acid.
- the precipitate thus formed is filtered on sintered glass and then dried under reduced pressure.
- the solid is reprecipitated in a methanol / water mixture to obtain 16.8 g (62.4 mmol) of a brown solid with a yield of 90%.
- Example 6 Synthesis of 3-methoxy-5 ', 6' -benzo-2,2'-cyclo [(2R, 4R) -pentandioxyl biphenyl.
- the reaction medium is stirred at -78 ° C for 1 h.
- 270 mg of copper cyanide (3mmol, l, 5eq.) In 30ml of THF are cannulas in lOmn. The agitation is maintained for 2 hours. A stream of bubble oxygen in the medium at -78 ° C for 2 h.
- the solution is brought up to ambient temperature then treated with a saturated solution of NH 4 C1.
- the reaction medium is extracted with 3 * 50ml of ether.
- the organic phase is dried over magnesium sulfate and then concentrated.
- the residue is chromatographed on silica gel (cyclohexane / ethyl acetate 9/1). 331 mg of a pale yellow solid are obtained with a yield of 50%.
- One of the two possible diastereoisomers is obtained by a large majority. It is isolated on its own after recrystallization.
- RMN E 3.71 (3H, s), 4.77 (1H, s), 5.26 (1H, s), 6.69 (1H, d, 8Hz), 6.79 (1H, d, 8Hz), 7.38 (5H, m), 7.95 (2H, m).
- the overall yield of the reaction is 60%.
- the enantiomeric purity of diphosphine has yet to be determined by HPLC.
- Example 14 Synthesis of 4, 5, 6-trimethyl-5 ', 6' - benzo-2, 2 '- biphenol.
- Example 17 Catalysis test. All catalysis tests were carried out according to the following method:
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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EP01996544A EP1341798A1 (fr) | 2000-11-17 | 2001-11-16 | Diphosphines chirales et leurs complexes metalliques |
US10/432,685 US20040138470A1 (en) | 2000-11-17 | 2001-11-16 | Chiral diphosphines and their metal complexes |
CA002429252A CA2429252A1 (fr) | 2000-11-17 | 2001-11-16 | Diphosphines chirales et leurs complexes metalliques |
AU2002220790A AU2002220790A1 (en) | 2000-11-17 | 2001-11-16 | Chiral diphosphines and their metal complexes |
JP2002543500A JP2004513951A (ja) | 2000-11-17 | 2001-11-16 | キラルジホスフィン及びその金属錯体 |
Applications Claiming Priority (2)
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FR0014895A FR2816946B1 (fr) | 2000-11-17 | 2000-11-17 | Diphosphines chirales dissymetriques, leurs utilisations pour la preparation de complexes diphosphino-metalliques, et les complexes diphosphino-metalliques ainsi obtenus |
FR00/14895 | 2000-11-17 |
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WO2002040492A1 true WO2002040492A1 (fr) | 2002-05-23 |
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PCT/FR2001/003607 WO2002040492A1 (fr) | 2000-11-17 | 2001-11-16 | Diphosphines chirales et leurs complexes metalliques |
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US (1) | US20040138470A1 (fr) |
EP (1) | EP1341798A1 (fr) |
JP (1) | JP2004513951A (fr) |
AU (1) | AU2002220790A1 (fr) |
CA (1) | CA2429252A1 (fr) |
FR (1) | FR2816946B1 (fr) |
WO (1) | WO2002040492A1 (fr) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1609795A1 (fr) * | 2004-06-25 | 2005-12-28 | Lonza AG | Procédé de préparation de Biaryldiphosphines asymétriquement substituées |
WO2006002730A1 (fr) * | 2004-06-25 | 2006-01-12 | Lonza Ag | Procede de preparation de biaryldiphosphines a substitution asymetrique |
WO2006002731A1 (fr) * | 2004-06-25 | 2006-01-12 | Lonza Ag | Procede pour preparer des biaryldiphosphines a substitution asymetrique |
US7312347B2 (en) | 2005-09-22 | 2007-12-25 | Takasago International Corporation | Substituted optically active disphosphine compound |
US7973182B2 (en) | 2004-02-19 | 2011-07-05 | Lonza Ltd. | Process for the preparation of enantiomerically pure 1-substituted-3-aminoalcohols |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP3406601B1 (fr) | 2016-07-29 | 2022-04-20 | LG Chem, Ltd. | Ligand multidirectionnel pour complexe organométallique |
KR101974184B1 (ko) | 2016-07-29 | 2019-04-30 | 주식회사 엘지화학 | 다방향성 리간드에 기반한 유기금속 복합체 |
Citations (4)
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EP0398132A2 (fr) * | 1989-05-18 | 1990-11-22 | F. Hoffmann-La Roche Ag | Composés du phosphore |
EP0690065A1 (fr) * | 1994-06-30 | 1996-01-03 | Hoechst Aktiengesellschaft | Biphenyl-2,2'-dyil-bis-diphenylphosphines halogénées, leur préparation et leur utilisation |
EP0749973A1 (fr) * | 1995-06-20 | 1996-12-27 | Bayer Ag | Nouvelles bisphosphines comme catalyseurs de réactions asymmétriques |
EP0826691A2 (fr) * | 1996-08-27 | 1998-03-04 | Takasago International Corporation | Composés diphosphines optiquement actives, procédé de leur préparation, complexes de métal de transition contenant ces composés comme ligand et procédé de préparation de substances optiquement actives par utilisation de ces complexes |
-
2000
- 2000-11-17 FR FR0014895A patent/FR2816946B1/fr not_active Expired - Fee Related
-
2001
- 2001-11-16 US US10/432,685 patent/US20040138470A1/en not_active Abandoned
- 2001-11-16 CA CA002429252A patent/CA2429252A1/fr not_active Abandoned
- 2001-11-16 WO PCT/FR2001/003607 patent/WO2002040492A1/fr not_active Application Discontinuation
- 2001-11-16 AU AU2002220790A patent/AU2002220790A1/en not_active Abandoned
- 2001-11-16 EP EP01996544A patent/EP1341798A1/fr not_active Withdrawn
- 2001-11-16 JP JP2002543500A patent/JP2004513951A/ja active Pending
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EP0398132A2 (fr) * | 1989-05-18 | 1990-11-22 | F. Hoffmann-La Roche Ag | Composés du phosphore |
EP0690065A1 (fr) * | 1994-06-30 | 1996-01-03 | Hoechst Aktiengesellschaft | Biphenyl-2,2'-dyil-bis-diphenylphosphines halogénées, leur préparation et leur utilisation |
EP0749973A1 (fr) * | 1995-06-20 | 1996-12-27 | Bayer Ag | Nouvelles bisphosphines comme catalyseurs de réactions asymmétriques |
EP0826691A2 (fr) * | 1996-08-27 | 1998-03-04 | Takasago International Corporation | Composés diphosphines optiquement actives, procédé de leur préparation, complexes de métal de transition contenant ces composés comme ligand et procédé de préparation de substances optiquement actives par utilisation de ces complexes |
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Title |
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MURATA M ET AL: "SYNTHESIS OF ATROPISOMERIC BIPHENYLBISOPHOSPINE, 6,2'-BIS (TRIFLUOROMETHYL)-1,1'-BIPHENYL (FUPMOP) AND ITS USE IN RUTHENIUM(II)-CATALYZED ASYMMETRIC HYDROGENATION OF A 3-OXO ESTER", SYNLETT, THIEME VERLAG, STUTTGART, DE, no. 11, 1 November 1991 (1991-11-01), pages 827 - 829, XP000604849, ISSN: 0936-5214 * |
SCHMID R ET AL: "Axially dissymmetric bis(triaryl)phosphines in the biphenyl series: synthesis of (6,6'-dimethylbiphenyl-2,2'-diyl)bis(diphenylph osphine) (BIPHEMP) and analogs, and their use in rhodium(I) catalyzed asymmetric isomerizations of N,N-diethylnerylamine", HELVETICA CHIMICA ACTA, VERLAG HELVETICA CHIMICA ACTA. BASEL, CH, vol. 71, no. 4, 1988, pages 897 - 929, XP002132237, ISSN: 0018-019X * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7973182B2 (en) | 2004-02-19 | 2011-07-05 | Lonza Ltd. | Process for the preparation of enantiomerically pure 1-substituted-3-aminoalcohols |
US8193380B2 (en) | 2004-02-19 | 2012-06-05 | Lonza Ag | Process for the preparation of enantiomerically pure 1-substituted-3-aminoalcohols |
US8198468B2 (en) | 2004-02-19 | 2012-06-12 | Lonza Ag | Process for the preparation of enantiomerically pure 1-substituted-3-aminoalcohols |
EP1609795A1 (fr) * | 2004-06-25 | 2005-12-28 | Lonza AG | Procédé de préparation de Biaryldiphosphines asymétriquement substituées |
WO2006002730A1 (fr) * | 2004-06-25 | 2006-01-12 | Lonza Ag | Procede de preparation de biaryldiphosphines a substitution asymetrique |
WO2006002729A1 (fr) * | 2004-06-25 | 2006-01-12 | Lonza Ag | Procede de preparation de biaryldiphosphines a substitution asymetrique |
WO2006002731A1 (fr) * | 2004-06-25 | 2006-01-12 | Lonza Ag | Procede pour preparer des biaryldiphosphines a substitution asymetrique |
US7312347B2 (en) | 2005-09-22 | 2007-12-25 | Takasago International Corporation | Substituted optically active disphosphine compound |
Also Published As
Publication number | Publication date |
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AU2002220790A1 (en) | 2002-05-27 |
FR2816946A1 (fr) | 2002-05-24 |
JP2004513951A (ja) | 2004-05-13 |
US20040138470A1 (en) | 2004-07-15 |
EP1341798A1 (fr) | 2003-09-10 |
CA2429252A1 (fr) | 2002-05-23 |
FR2816946B1 (fr) | 2004-04-02 |
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