JP4805577B2 - キラル遷移金属触媒、及び該触媒を用いるキラル有機化合物の接触製造法 - Google Patents
キラル遷移金属触媒、及び該触媒を用いるキラル有機化合物の接触製造法 Download PDFInfo
- Publication number
- JP4805577B2 JP4805577B2 JP2004543948A JP2004543948A JP4805577B2 JP 4805577 B2 JP4805577 B2 JP 4805577B2 JP 2004543948 A JP2004543948 A JP 2004543948A JP 2004543948 A JP2004543948 A JP 2004543948A JP 4805577 B2 JP4805577 B2 JP 4805577B2
- Authority
- JP
- Japan
- Prior art keywords
- chiral
- ligand
- monophosphorous
- ligands
- transition metal
- 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 61
- 229910052723 transition metal Inorganic materials 0.000 title claims description 34
- 150000003624 transition metals Chemical class 0.000 title claims description 34
- 150000002894 organic compounds Chemical class 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title description 9
- 230000003197 catalytic effect Effects 0.000 title description 2
- 239000003446 ligand Substances 0.000 claims description 113
- 238000005984 hydrogenation reaction Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 150000001408 amides Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 150000003346 selenoethers Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 53
- 229910015892 BF 4 Inorganic materials 0.000 description 52
- 239000010948 rhodium Substances 0.000 description 50
- 239000000203 mixture Substances 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 229910052794 bromium Inorganic materials 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 8
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- -1 monophosphorus compound Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 0 **OC(C=CC1C2C=CCC1)=C2c(c(cccc1)c1cc1)c1P Chemical compound **OC(C=CC1C2C=CCC1)=C2c(c(cccc1)c1cc1)c1P 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 125000004437 phosphorous atom Chemical group 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001470 diamides Chemical class 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 238000007037 hydroformylation reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 150000003003 phosphines Chemical class 0.000 description 4
- 125000005538 phosphinite group Chemical group 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- 229910052768 actinide Inorganic materials 0.000 description 3
- 150000001255 actinides Chemical class 0.000 description 3
- 238000006668 aldol addition reaction Methods 0.000 description 3
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 3
- 238000006757 chemical reactions by type Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005888 cyclopropanation reaction Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000033444 hydroxylation Effects 0.000 description 3
- 238000005805 hydroxylation reaction Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011814 protection agent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- LYXHWHHENVLYCN-QMDOQEJBSA-N (1z,5z)-cycloocta-1,5-diene;rhodium;tetrafluoroborate Chemical compound [Rh].F[B-](F)(F)F.C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 LYXHWHHENVLYCN-QMDOQEJBSA-N 0.000 description 2
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- 238000006411 Negishi coupling reaction Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000006399 aminohydroxylation reaction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 238000005913 hydroamination reaction Methods 0.000 description 2
- 238000006197 hydroboration reaction Methods 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000006267 hydrovinylation reaction Methods 0.000 description 2
- 238000006713 insertion reaction Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- QHHCNGMCBLWAJB-UHFFFAOYSA-N 3-chloro-6-(4-chloro-2-hydroxy-3-methoxyphenyl)-2-methoxyphenol Chemical compound C1=C(Cl)C(OC)=C(O)C(C=2C(=C(OC)C(Cl)=CC=2)O)=C1 QHHCNGMCBLWAJB-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- ULBXWWGWDPVHAO-UHFFFAOYSA-N Chlorbufam Chemical compound C#CC(C)OC(=O)NC1=CC=CC(Cl)=C1 ULBXWWGWDPVHAO-UHFFFAOYSA-N 0.000 description 1
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- VVBXKASDRZXWON-UHFFFAOYSA-N N=[PH3] Chemical class N=[PH3] VVBXKASDRZXWON-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- OWVIRVJQDVCGQX-VSGBNLITSA-N [(4r,5r)-5-[hydroxy(diphenyl)methyl]-2,2-dimethyl-1,3-dioxolan-4-yl]-diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)([C@H]1[C@@H](OC(O1)(C)C)C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 OWVIRVJQDVCGQX-VSGBNLITSA-N 0.000 description 1
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical class PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- JYHHJVKGDCZCCL-UHFFFAOYSA-J carbon monoxide;dichlororuthenium Chemical compound [O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].Cl[Ru]Cl.Cl[Ru]Cl JYHHJVKGDCZCCL-UHFFFAOYSA-J 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000004697 chelate complex Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZLRAAUUPULJGTL-UHFFFAOYSA-N diaminophosphinous acid Chemical class NP(N)O ZLRAAUUPULJGTL-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- IHPDTPWNFBQHEB-UHFFFAOYSA-N hydrobenzoin Chemical compound C=1C=CC=CC=1C(O)C(O)C1=CC=CC=C1 IHPDTPWNFBQHEB-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000000057 phosphinines Chemical class 0.000 description 1
- 150000008300 phosphoramidites Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- WSANLGASBHUYGD-UHFFFAOYSA-N sulfidophosphanium Chemical class S=[PH3] WSANLGASBHUYGD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
- B01J31/1855—Triamide derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
- B01J31/187—Amide derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—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
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
- C07F9/65842—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
- C07F9/65842—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring
- C07F9/65844—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring the phosphorus atom being part of a five-membered ring which may be condensed with another ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
- C07F9/65848—Cyclic amide derivatives of acids of phosphorus, in which two nitrogen atoms belong to the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
- B01J2231/325—Cyclopropanations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
- B01J2231/326—Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
- B01J2231/327—Dipolar cycloadditions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/348—1,4-additions, e.g. conjugate additions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4238—Negishi-type, i.e. RY + R'ZnZ, in which R, R' is optionally substituted alkyl, alkenyl, alkynyl, aryl, Y is the leaving group and Z is halide or R'
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4255—Stille-type, i.e. RY + R'3SnR'', in which R is alkenyl, aryl, R' is alkyl and R'' is alkenyl or aryl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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"
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/506—Method of making inorganic composition utilizing organic compound, except formic, acetic, or oxalic acid or salt thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、2またはそれ以上のキラルなモノホスフォラス化合物(1個のリン原子を有する化合物)の混合物、又は少なくとも1つのキラルと少なくとも1つのアキラルモノホスフォラス化合物からなる混合物は、不斉遷移金属触媒において優れた配位子系を構成するという驚くべき発見を含む。これらは、公知又は新規なキラルモノホスフォラス化合物が用いられるエナンチオ選択性遷移金属触媒の分野において基本的に新規なプロセスである。尚、2個の(又はそれ以上の)異なるモノホスフォラス化合物が金属と結合していて、そのうち少なくとも1つはキラルモノホスフォラス化合物である、このようなキラル遷移金属触媒は、構造的に新規なタイプである。このような金属錯体はこれまで文献においても記述されていない。
この目的のために必要とされる配位子は、しばしばキラルなホスフォラス配位子(P配位子)、すなわちホスフィン(phosphines)、ホスフォナイト(phosphonites)、ホスフィナイト(phosphinites)、ホスファイト(phosphites)、又はホスフォアミディティ(phosphoramidites)であり、これらは遷移金属に結合している。典型的な例は、BINAP(例えば、非特許文献4参照)、DuPHOS(例えば、非特許文献5参照)、BICP(例えば、非特許文献6参照)、及びBPE(例えば、非特許文献7参照)のような光学活性なロジウム、ルテニウム又はイリジウム錯体を含む。キラル配位子の発展は、設計と試行錯誤からなる高価なプロセスを伴う(例えば、非特許文献2参照)。
あいにく、この方法には制限が存在する、すなわち、多くの基質(substrate)は、例えば水素付加反応又はヒドロホルミル化反応において、中程度か低いエナンチオ選択率で変化する。それ故、依然として遷移金属触媒に工業的に適用するために安価で効果的なキラル配位子が必要とされている。
実施態様1においては、更に下記(2)ないし(11)の態様とすることが望ましい。
(2)上記項目(1)に記載した触媒において、1つのモノホスフォラス配位子が厳密にキラルであること、
(3)上記項目(1)に記載した触媒において、少なくとも2つのモノホスフォラス配位子がキラルであること、
ここで、X、Y及びZはまた結合原子又は原子基により他と結合されていてもよく、
X−P−Yはまた芳香族系の一部をなし、この場合XはPと二重結合で結合されていて置換基Zが存在していなくともよい。
(5)前記項目(1)ないし(3)に記載した遷移金属触媒において、モノホスフォラス配位子がホスフィン(phosphines)、ホスファイト(phosphites)、ホスフォナイト(phosphonites)、ホスフィナイト(phosphinites)、ホスフォラストリアミド(phosphorous triamides)、ホスフォラスモノエステルジアミド(phosphorous monoester diamides)、ホスフォラスジエステルアミド(phosphorous diester amides)、ホスフォナスジアミド(phosphonous diamides)、ホスフィナスアミド(phosphinous amides)、ホスフォナスモノエステルアミド(phosphonous monoester amides)、ホスフォラスハライド(phosphorous halides)、ホスフォラスジアミドハライド(phosphorous diamide halides)、チオホスファイト(thiophosphites)、チオホスフォラストリエステル(thiophosphorous triesters)、チオホスフォラスモノエステルジアミド(thiophosphorous monoester diamides)、又はチオホスフォラスジエステルアミド(thiophosphorous diesteramides)であること、
そして、ここでR1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R5’、R6’、R7’及びR8’ラジカルは、それぞれ独立に水素、ハロゲン、飽和及び不飽和、直鎖状及び分岐状のC1−C50アルキル(alkyl)、C1−C50アリール(aryl)、C1−C50ヘテロアリール(heteroaryl)、アルキニル(alkynyl)、シリル(silyl)、ニトロ(nitro)、ニトリル(nitrile)、エステル(ester)、カルボキシル(carboxyl)、カルボニル(carbonyl)、アミド(amide)、アミン(amine)、ヒドロキシル(hydroxyl)、アルコキシ(alkoxy)、スルフィド(sulfide)及びセレナイド(selenide)基の群からなり、
ここでR1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R5’、R6’、R7’及びR8’は、同様に更に置換基を有していてもよく、また官能基とされていてもよい、
そしてビナフチル構造の1またはそれ以上の炭素原子はヘテロ原子Si、O、N又はSで置換することもできる。
そしてここで、R1、R2、R3、R4、R5、R6、R1’、R2’、R3’、R4’、R5’及びR6’ラジカルはそれぞれ独立に水素、ハロゲン、飽和及び不飽和、直鎖状及び分岐状のC1−C50アルキル(alkyl)、C1−C50アリール(aryl)、C1−C50ヘテロアリール(heteroaryl)、アルキニル(alkynyl)、シリル(silyl)、ニトロ(nitro)、ニトリル(nitrile)、エステル(ester)、カルボキシル(carboxyl)、カルボニル(carbonyl)、アミド(amide)、アミン(amine)、ヒドロキシル(hydroxyl)、アルコキシ(alkoxy)、スルフィド(sulfide)並びにセレナイド(selenide)基の群からなり、
ここでR1、R2、R3、R4、R5、R6、R1’、R2’、R3’、R4’、R5’及びR6’は、同様に更に置換基を有していてもよく、また官能基とされていてもよい、
そしてここで、ビナフチル構造の1またはそれ以上の炭素原子はそれぞれ独立にヘテロ原子Si、O、N又はSで置換されていてもよい。
ここでR1、R2、R3及びR4は、同様に更に置換基を有していてもよくまた官能基とされていても架橋されていてもよい。
(9)上記項目(1)ないし(8)に記載した遷移金属触媒において、遷移金属が周期律表のIIIb、IVb、Vb、VIb、VIIb、VIII、IbもしくはIIb、又はランタニドもしくはアクチノイドであること、
(10)前記項目(9)の触媒において、遷移金属がRh、Ir、Ru、Ni、Pd又はPtであること、
実施態様2においては、更に下記(13)ないし(15)の態様とすることが望ましい。
(13)前記項目(12)の製造法において、化学反応が水素付加反応(hydrogenation)であること、
(14)前記項目(12)の製造法において、化学反応がヒドロホルミル化反応(hydroformylation)であること、
(15)前記項目(12)の製造法において、化学反応がヒドロホウ素化(hydroboration)、ヒドロシリル化(hydrosilylation)、ヒドロビニル化(hydrovinylation)、ヒドロアミノ化(hydroamination)、エポキシド化(epoxidation)、ヒドロキシル化(hydroxylation)、アミノヒドロキシル化(aminohydroxylation)、置換反応(substitution)、アリル置換反応(allyl substitution)、ヘックカップリング(Heck coupling)、スチルカップリング(Stille coupling)、鈴木カップリング(Suzuki coupling)、根岸カップリング(Negishi coupling)、ミッシェル付加(Michael addition)、アルドール付加(aldol addition)、ジールス−アルダー反応(Diels-Alder reaction)、シクロプロパネーション(cyclopropanation)、CHインサート反応(CH insertion reaction)、又は1,3−双極環状付加反応(1,3-dipolar cycloaddition)であること。
本発明者らが用いる、少なくとも2つの異なるモノホスフォラス配位子(すなわち、1個のリン原子を有する化合物である)が金属原子に結合していて、少なくとも1個のモノホスフォラス配位子がキラルであるこれらの遷移金属触媒は、新規である。これらの触媒は、プロキラル有機化合物からキラル有機化合物を製造する際に多くの異なる反応の種類に用いることができる。光学的に豊富化された又は純粋な有機化合物は、工業的に有用な製品又は、中間製品として知られている、例えば医薬品、農作物保護薬及びフラグランス等が挙げられる。
このような配位条件は周期律表のIIIb、IVb、Vb、VIb、VIIb、VIIIb、Ib及びIIbグループの金属で、並びにランタノイドとアクチノイドで知られている。例えば、2種類のこのような配位子LaとLbの混合物の場合、3つの異なる触媒が平衡状態で存在することが、特に従来の同種組合せ(以下単に「同種組合せ(homocombination)」ということがある。)MLaLaとMLbLb、及び新規な異種組合せ(以下単に「異種組合せ(heterocombination)」ということがある。)MLaLb(混合触媒)で可能である。文献で、同種組合せ多くの例が見いだされる、最近の例では、バイノールからモジュール的に形成される、モノホスフォナイト(monophosphonites)I、モノホスファイト(monophosphites)II、及びモノホスフォアミディティ(monophosphoramidites)IIIが知られており、これらのそれぞれはしばしば(常にではないが)Rh−触媒によるオレフィンの水素付加反応において高いエナンチオ選択性を可能にする。
一方、異種組合せMLaLbはこれまで触媒として記述されていない。一般に迅速な配位子交換が進行するので、溶液から純粋なMLaLbを発生させることは相当に困難である。しかし、MLaLbが純粋な形態で用いられる触媒MLaLaとMLbLbより迅速で高いエナンチオ選択性を示す場合には、3種の触媒の混合物でも、高いエナンチオ選択性をもたらし、そして配位子LaとLbの相対量は同様に重要な役割を果たす。
X、Y及びZはまた結合原子又は原子基により他と結合されていてもよく、そしてX−P−Yはまた芳香族系の一部をなしてもよい、この場合、XはPと二重結合で結合されていて置換基Zは存在しない。
a)X=Y=Z=C
b)X=Y=C;Z=N
c)X=Y=C;Z=O
d)X=Y=C;Z=S
e)X=Y=C;Z=ハロゲン(F、Cl、Br又はI)
f)X=C;Y=Z=N
g)X=C;Y=Z=O
h)X=C;Y=Z=S
i)X=C;Y=N; Z=O
j)X=Y=Z=N
k)X=Y=N; Z=O
l)X=Y=N; Z=S
m)X=Y=N; Z=ハロゲン(F、Cl、Br又はI)
n)X=N; Y=Z=O
o)X=N; Y=Z=S
p)X=N; Y=O; Z=ハロゲン(F、Cl、Br又はI)
q)X=Y=Z=O
r)X=Y=O; Z=ハロゲン(F、Cl、Br又はI)
s)X=Y=Z=S
しかしながら、これらは可能性のあるいものをいくつか挙げたにすぎないが、その説明が可能性の範囲を決して制限するものではない。配位子IVはモジュール的に形成されているので、このことは、特有の構成単位が例えば最も重要なものを挙げればキラルアルコール、キラルジオール、キラルアミン、キラルジアミン又はキラルアミノアルコールであることを意味する。
次に示す例において、完全にキラルなものは例示していない。しかし、どのような配位子がどのような可能な構造に用いられるかは自明である。配位子は、エナンチオメリカリー(enantiomerically)に純粋であるか、富化された形態で用いられる。好ましいのは、エナンチオメリカリーに純粋なものを利用することである。
同様に、本発明の第2の変形例は、2つの異なるホスフォラス配位子を含み、その1つは(上記で記述したように)キラルなものを含むが他はアキラルである。
配位子IVとアキラルな類似体IVの好適な組合せの使用は、遷移金属触媒をもたらし、このような場合、適切な1つのキラル配位子のみを用いる場合よりも極めて高いエナンチオ選択性が得られる。ある場合、このような組合せは、エナンチオ選択性の方向を逆にするのに用いることができる。
代表的な例をいくつか挙げれば、Rh(COD)2BF4、 [(cymene)RuCl2]2、 (pyridine)2Ir(COD)BF4、 Ni(COD)2、 (TMEDA)Pd(CH3)2 (TEMDA=N,N,N’,N’-テトラメチレンジアミン), Pt(COD)2, PtCl2(COD)又は[RuCl2(CO)3]2がある。金属は、周期律表のIIIb、IVb、Vb、VIb、VIIb、VIII、Ib、及びIIb、並びにランタノイドとアクチノイドの群を含む。
実際の適用に関しては、“混合された錯体”XXIXは純粋な錯体XXVII及びXXVIIIから分離される必要はない、なぜなら動力学的研究に基づいて、3種の触媒の混合物は個々の同種組み合わせXXVIIとXXVIIIよりも活性が高いということが見出されるからである。同様に他の“混合された”金属触媒(異種組み合わせ)の類似のNMRとEMS−MS分析は、これらの錯体独自の構造を示し、それは新しい物質の種類であることを証明している。
鏡像体過剰率(enantiomeric excess)を測定するために、反応溶液の約1.5mlを小さなシリカゲルを通して吸着ろ過し、ガスクロマトグラフィー又は高速液体クロマトグラフィー(HPLC)を用いて分析した。実験は、20個の容器を用いて並列に行った。
比較のために、純粋な配位子が他の同様な条件下でRh触媒による水素付加反応においてテストされた。結果をテーブル1にまとめて示す。これらの結果から、実際にいくつかの混合触媒(異質組合せ)は明らかに従来型の純粋な配位子(エントリー番号1−14)から形成される類似物よりもエナンチオ選択率(例えばエントリー番号16、17、40、42、44及び45)が高い。
鏡像体過剰率を測定するために、反応溶液の約1.5mlを小さなシリカゲルを通して吸着ろ過し、ガスクロマトグラフィー又は高速液体クロマトグラフィー(HPLC)を用いて分析した。実験は、20個の容器を用いて並列に行った。
100%の転化率で測定したエナンチオ選択率は、以下の通りであった。
(R)Ia/(R)Ic: ee=96.7%(S)
(R)Ia/(R)Id: ee=99.2%(S)
(R)Ib/(R)Id: ee=94.6%(S)
比較の例
(R)Ia/(R)Ia: ee=89.9%(S)
(R)Ib/(R)Ib: ee=89.2%(S)
(R)Id/(R)Id: ee=69.1%(S)
(R)Ia/(R)Id: ee=95.0%(S)
比較の例
(R)Ia/(R)Ia: ee=73.0%(S)
(R)Id/(R)Id: ee=16.2%(S)、転化率79%
Rh-触媒による1-N-アシルアミノスチレンの水素付加反応における2つのホスフォラス配位子IaとIdの比の変化
配位子IaとIdの相対比を変えて、実施例3における水素付加反応を行った。
Rh:P比を1:2、Rh:基質比を1:500で一定とした。95%以上の転化率でGC手段により測定したエナンチオ選択率をテーブル2にまとめて示す。
(R)Ia/(R)Id: ee=97.0%(S)
比較の例
(R)Ia/(R)Ia: ee=78.2%(S)
(R)Id/(R)Id: ee=<3%(S)、転化率35%
Rh:基質=1:6000でee値は95.8%(R)、同様に1:10000でee値は95.4%(R)、同様に1:20000でee値は94.6%(R)であった。
触媒系Rh[Ia][Id][COD]BF4+Rh[Ia]2[COD]BF4+Rh[Id]2[COD]BF4の調製と特性
CD2Cl2(1ml)中の(R)Ia(13.2mg;0.04mmol)及び(R)Id(14.9mg;0.04mmol)の混合物をCD2Cl2(1ml)中のRh[COD]2BF4(16.2mg;0.04mmol)で処理した。
1H、13C及び31PのNMRスペクトルは、2つの同種組合せ Rh[(R)Ia]2[COD]BF4 (XXVII)とRh[(R)Id]2[COD]BF4(XXVIII)、及び異種組合せRh[(R)Ia][(R)Id]BF4 (XXIX)が約20:20:60の割合で存在していることを示す。31Pにおける特有のピークと分布は以下の通りである。
ESI−MSによる触媒系Rh[Ia][Id][COD]BF4+Rh[Ia]2[COD]BF4 +Rh[Id]2[COD]BF4の調製、分離及び特性
CH2Cl2(20 ml)中の(R)Ia(32.6mg;0.1mmol)及び(R)Id(36.9mg;0.1 mmol)の混合物をCH2Cl2(5 ml)中のRh[COD]2BF4(40.7mg;0.1mmol)と−78℃で混合した。室温まで暖めた後、溶媒を5mlまで濃縮し、黄色の固体を15mlのペンタンで沈殿させた。この結晶をペンタンで3度洗浄し、減圧下に乾燥させた。ESI−MSスペクトルで、実施例9に記載した錯体のフラグメントが検出された、これは主な成分を形成する異種組み合わせの錯体XXIXであった。CD2Cl2溶媒内の31NMRスペクトルは、実施例9ですでに記述し決定されたのと同じシグナルを示した。
Rh[(R)Ia]2[COD]BF4(XXVII):
MS(ESI/pos.in CH2Cl2):m/z=763[M+-BF4-COD].
Rh[(R)Id]2[COD]BF4(XXVIII):
MS(ESI/pos.in CH2Cl2):m/z=847[M+-BF4-COD].
Rh[(R)Ia][(R)Id][COD]BF4(XXIX):
MS(ESI/pos.in CH2Cl2):m/z=805[M+-BF4-COD].
Rh[Ia]2[COD]BF4とRh[Id]2[COD]BF4の混合物の分析
Rh[Ia]2[COD]BF4(3.3mg; 0.0034mmol;0.5 mlのCD2Cl2)の溶液と
Rh[Id]2[COD]BF4(3.5mg; 0.0034mmol;0.5mlのCD2Cl2)の溶液を混合した。この混合物を31PNMRスペクトロスコピー法で分析した。シグナル(実施例9に類似)を参照して、同じ成分Rh[(R)Ia]2[COD]BF4 (XXVII)、Rh[(R)Id]2[COD]BF4(XXVIII)及びRh[(R)Ia][(R)Id]BF4 (XXIX)が実施例9におけると同様に存在することが見出された。
ESI−MSによる触媒系Rh[Ia][Ic][COD]BF4+Rh[Ia]2[COD]BF4 +Rh[Ic]2[COD]BF4の調製、分離及び特性
CH2Cl2(20 ml)中の(R)Ia(29.4mg;0.09mmol)及び(R)Ic(36.5mg;0.09 mmol)の混合物をCH2Cl2(5 ml)中のRh[COD]2BF4(40.7mg;0.09mmol)と−78℃で混合した。室温まで暖めた後、溶媒を5mlまで濃縮し、黄色の固体を15mlのペンタンで沈殿させた。この結晶をペンタンで3度洗浄し、減圧下に乾燥させた。ESI−MSスペクトルで以下のフラグメントが検出された。
Rh[(R)Ia]2[COD]BF4:
MS(ESI/pos.in CH2Cl2):m/z=763[M+-BF4-COD].
Rh[(R)Ic]2[COD]BF4:
MS(ESI/pos.in CH2Cl2):m/z=897[M+-BF4-COD-2H].
Rh[(R)Ia][(R)Ic][COD]BF4:
MS(ESI/pos.in CH2Cl2):m/z=831[M+-BF4-COD].
ESI−MSによる触媒系Rh[IIa][Ic][COD]BF4+Rh[IIa]2[COD]BF4 +Rh[Ic]2[COD]BF4の調製、分離及び特性
CH2Cl2(20 ml)中の(R)IIa(44.6mg;0.13mmol)及び(R)Ic(51.8mg;0.13 mmol)の混合物をCH2Cl2(5 ml)中のRh[COD]2BF4(52.8mg;0.13mmol)と−78℃で混合した。室温まで暖めた後、溶媒を5mlまで濃縮し、黄色の固体を15mlのペンタンで沈殿させた。この結晶をペンタンで3度洗浄し、減圧下に乾燥させた。ESI−MSスペクトルで以下のフラグメントが検出された。
Rh[(R)IIa]2[COD]BF4:
MS(ESI/pos.in CH2Cl2):m/z=795[M+-BF4-COD].
Rh[(R)Ic]2[COD]BF4:
MS(ESI/pos.in CH2Cl2):m/z=897[M+-BF4-COD-2H].
Rh[(R)IIa][(R)Ic][COD]BF4:
MS(ESI/pos.in CH2Cl2):m/z=845[M+-BF4-COD-2H].
Claims (3)
- キラル遷移金属触媒の存在下でのプロキラル有機化合物の水素付加のための方法において、
少なくとも2つの構造的に異なるモノホスフォラス配位子が、遷移金属としてのRhに結合しているとともに、少なくとも2つのキラルなモノホスフォラス配位子を含み、かつ、
前記キラルなモノホスフォラス配位子が、下式Iのモノホスフォナイト及び下式IIのモノホスファイト
ここで、式I及び式II中のビナフチル基は、それぞれ独立に、ハロゲン、飽和及び不飽和、直鎖状及び分岐状のC1−C50アルキル、C1−C50アリール、C1−C50ヘテロアリール、アルキニル、シリル、ニトロ、ニトリル、エステル、カルボキシル、カルボニル、アミド、アミン、ヒドロキシル、アルコキシ、スルフィド、並びにセレナイド基の群から選択された置換基を有していてもよく、かつ、
前記2つの構造的に異なるモノホスフォラス配位子の組み合わせが、(R)Ia/(R)Ic、(R)Ia/(R)Id、(R)Ic/(R)Id、(R)IIa/(R)IIf、(R)Ic/(R)IIa、(R)Id/(R)IIa、(R)Id/(R)IIh、又は(R)Ic/(R)IIhである、
ことを特徴とする方法。 - キラル遷移金属触媒の存在下でのプロキラル有機化合物の水素付加のための方法において、
少なくとも2つの構造的に異なるモノホスフォラス配位子が遷移金属としてのRhに結合しているとともに、少なくとも1つのキラルなモノホスフォラス配位子と、少なくとも1つのアキラルなモノホスフォラス配位子とを含み、
前記キラルなモノホスフォラス配位子が、下式Iのモノホスフォナイト又は下式IIのモノホスファイト
ここで、式I及び式II中のビナフチル基は、それぞれ独立に、ハロゲン、飽和及び不飽和、直鎖状及び分岐状のC 1 −C 50 アルキル、C 1 −C 50 アリール、C 1 −C 50 ヘテロアリール、アルキニル、シリル、ニトロ、ニトリル、エステル、カルボキシル、カルボニル、アミド、アミン、ヒドロキシル、アルコキシ、スルフィド、並びにセレナイド基の群から選択された置換基を有していてもよく、かつ、
前記のアキラルなモノホスフォラス配位子が下式H又は式Tタイプのモノホスフォラス化合物であり、
前記キラルなモノホスフォラス配位子と前記アキラルなモノホスフォラス配位子の組み合わせが、(R)Ia/Hタイプ、(R)IIa/Hタイプ、(R)IId/Hタイプ、(R)Ia/Tタイプ、又は(R)Id/Tタイプである、
ことを特徴とする方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10247633.0 | 2002-10-11 | ||
DE10247633A DE10247633A1 (de) | 2002-10-11 | 2002-10-11 | Mischungen von chiralen Monophosphor-Verbindungen als Ligandensysteme für die asymmetrische Übergangsmetallkatalyse |
PCT/DE2003/003226 WO2004035208A1 (de) | 2002-10-11 | 2003-09-26 | Mischungen von chiralen monophosphor-verbindungen als liganden-systeme für die asymmetriche übergangsmetall-katalyse |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2006502843A JP2006502843A (ja) | 2006-01-26 |
JP2006502843A5 JP2006502843A5 (ja) | 2010-03-18 |
JP4805577B2 true JP4805577B2 (ja) | 2011-11-02 |
Family
ID=32049245
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004543948A Expired - Fee Related JP4805577B2 (ja) | 2002-10-11 | 2003-09-26 | キラル遷移金属触媒、及び該触媒を用いるキラル有機化合物の接触製造法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US7704912B2 (ja) |
EP (1) | EP1558384B1 (ja) |
JP (1) | JP4805577B2 (ja) |
AU (1) | AU2003269835A1 (ja) |
CA (1) | CA2501373C (ja) |
DE (1) | DE10247633A1 (ja) |
DK (1) | DK1558384T3 (ja) |
WO (1) | WO2004035208A1 (ja) |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT501193B1 (de) | 2004-12-27 | 2007-03-15 | Dsm Fine Chem Austria Gmbh | Verfahen zur übergangsmetall - katalysierten asymmetrischen hydrierung von acrylsäurederivaten |
US8039122B2 (en) | 2005-03-28 | 2011-10-18 | Semiconductor Energy Laboratory Co., Ltd. | Anthracene derivative, material for light emitting element, light emitting element, light emitting device, and electronic device |
US7731377B2 (en) * | 2006-03-21 | 2010-06-08 | Semiconductor Energy Laboratory Co., Ltd. | Backlight device and display device |
WO2007134446A1 (en) * | 2006-05-23 | 2007-11-29 | The University Of Western Ontario | High-throughput screening of enantiomeric excess (ee) |
CN101506163B (zh) * | 2006-08-30 | 2012-05-02 | 株式会社半导体能源研究所 | 合成蒽衍生物的方法和蒽衍生物、发光元件、发光装置、电子装置 |
US20080190352A1 (en) * | 2007-02-12 | 2008-08-14 | Daewoo Shipbuilding & Marine Engineering Co., Ltd. | Lng tank ship and operation thereof |
US7723722B2 (en) * | 2007-03-23 | 2010-05-25 | Semiconductor Energy Laboratory Co., Ltd. | Organic compound, anthracene derivative, and light-emitting element, light-emitting device, and electronic device using anthracene derivative |
US20080286445A1 (en) * | 2007-05-17 | 2008-11-20 | Semiconductor Energy Laboratory Co., Ltd. | Composition, and method of fabricating light-emitting element |
WO2010005066A1 (en) * | 2008-07-08 | 2010-01-14 | Semiconductor Energy Laboratory Co., Ltd. | Carbazole derivative, light-emitting element material, light-emitting element, and light-emitting device |
ATE517088T1 (de) * | 2008-09-19 | 2011-08-15 | Semiconductor Energy Lab | Carbazolderivat und herstellungsverfahren dafür |
SG10201505698TA (en) | 2009-03-04 | 2015-09-29 | Chevron Phillips Chemical Co | Selective hydrogenation catalyst and methods of making and using same |
US9834856B2 (en) * | 2012-01-06 | 2017-12-05 | Iowa State University Research Foundation, Inc. | Controlled fabrication of semiconductor-metal hybrid nano-heterostructures via site-selective metal photodeposition |
EP2829546A3 (de) * | 2013-07-23 | 2015-05-06 | Evonik Industries AG | Isomerisierungsarme Hydroformylierung von Ölsäureester-haltigen Gemischen |
US10320722B2 (en) * | 2014-10-23 | 2019-06-11 | Level 3 Communications, Llc | Subscription/notification of a conference in a collaboration conferencing system |
ES2670039T3 (es) * | 2014-12-04 | 2018-05-29 | Evonik Degussa Gmbh | Monofosfitos que presentan un componente biarilo asimétrico |
CN104725427B (zh) * | 2015-02-03 | 2017-06-16 | 商丘师范学院 | 分子内c‑h芳基化反应催化合成手性膦化合物及其制备方法 |
KR20170101128A (ko) | 2016-02-26 | 2017-09-05 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 유기 화합물, 발광 소자, 발광 장치, 전자 기기, 및 조명 장치 |
CN105728047B (zh) * | 2016-03-24 | 2017-12-26 | 万华化学集团股份有限公司 | 一种氢甲酰化催化剂及其制备方法和应用 |
EP3301087A1 (en) | 2016-09-30 | 2018-04-04 | DPx Fine Chemicals Austria GmbH & Co KG | Process for preparing chiral amines |
CN110280304B (zh) * | 2019-07-09 | 2022-07-05 | 华东师范大学 | 一类手性氨基醇衍生的磷酰胺-胺双功能催化剂及其三步一锅合成方法 |
CN111205328B (zh) * | 2020-02-27 | 2021-07-13 | 上海交通大学 | 一种手性硫/硒化合物及其制备方法和应用 |
CN114685564B (zh) * | 2020-12-27 | 2023-09-22 | 西北大学 | 新型亚磷酰胺配体及其合成方法和应用 |
CN114478337B (zh) * | 2022-01-30 | 2023-11-28 | 安徽泽升科技有限公司上海分公司 | 一种轴手性含硫双芳基衍生物及其合成方法 |
CN114605458A (zh) * | 2022-05-03 | 2022-06-10 | 上海毕得医药科技股份有限公司 | 一种过渡金属催化环丙烷碳碳键活化制备手性γ-氨基硼酸酯的方法 |
CN115197271B (zh) * | 2022-09-06 | 2022-12-09 | 泽升科技(广州)有限公司 | 一类基于1,2-二芳基-1,2-乙二醇(胺)的硒/硫类化合物及其合成方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5543536A (en) * | 1994-04-26 | 1996-08-06 | E. I. Du Pont De Nemours And Company | Monodentate phosphite and nickel catalyst composition for monoolefin hydrocyanation |
JP2966094B2 (ja) * | 1991-08-21 | 1999-10-25 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー コーポレイション | 不斉合成 |
US6232263B1 (en) * | 1998-10-16 | 2001-05-15 | Eastman Chemical Company | Hydroformylation process using novel phosphite-metal catalyst system |
WO2001094278A1 (de) * | 2000-06-06 | 2001-12-13 | Studiengesellschaft Kohle Mbh | Chirale monophosphite als liganden für die asymmetrische übergangsmetall-katalysierte hydrierung |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8802611A (nl) * | 1988-10-24 | 1990-05-16 | Shell Int Research | Katalysatorcomposities. |
NL1015655C2 (nl) * | 2000-07-07 | 2002-01-08 | Dsm Nv | Katalysator voor de asymmetrische hydrogenering. |
-
2002
- 2002-10-11 DE DE10247633A patent/DE10247633A1/de not_active Ceased
-
2003
- 2003-09-26 US US10/530,818 patent/US7704912B2/en not_active Expired - Fee Related
- 2003-09-26 WO PCT/DE2003/003226 patent/WO2004035208A1/de active Application Filing
- 2003-09-26 AU AU2003269835A patent/AU2003269835A1/en not_active Abandoned
- 2003-09-26 CA CA2501373A patent/CA2501373C/en not_active Expired - Fee Related
- 2003-09-26 EP EP03750375.2A patent/EP1558384B1/de not_active Expired - Lifetime
- 2003-09-26 JP JP2004543948A patent/JP4805577B2/ja not_active Expired - Fee Related
- 2003-09-26 DK DK03750375.2T patent/DK1558384T3/en active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2966094B2 (ja) * | 1991-08-21 | 1999-10-25 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー コーポレイション | 不斉合成 |
US5543536A (en) * | 1994-04-26 | 1996-08-06 | E. I. Du Pont De Nemours And Company | Monodentate phosphite and nickel catalyst composition for monoolefin hydrocyanation |
JPH09512534A (ja) * | 1994-04-26 | 1997-12-16 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | モノオレフィンヒドロシアン化用の一座ホスファイトとニッケルの触媒組成物 |
US6232263B1 (en) * | 1998-10-16 | 2001-05-15 | Eastman Chemical Company | Hydroformylation process using novel phosphite-metal catalyst system |
WO2001094278A1 (de) * | 2000-06-06 | 2001-12-13 | Studiengesellschaft Kohle Mbh | Chirale monophosphite als liganden für die asymmetrische übergangsmetall-katalysierte hydrierung |
JP2003535834A (ja) * | 2000-06-06 | 2003-12-02 | シュトゥディエンゲゼルシャフト・コーレ・ミット・ベシュレンクテル・ハフツング | 不斉合成のためのリガンドとしてのキラルなモノホスファイト |
Also Published As
Publication number | Publication date |
---|---|
DK1558384T3 (en) | 2015-06-29 |
JP2006502843A (ja) | 2006-01-26 |
EP1558384B1 (de) | 2015-03-25 |
US20060014981A1 (en) | 2006-01-19 |
EP1558384A1 (de) | 2005-08-03 |
CA2501373A1 (en) | 2004-04-29 |
AU2003269835A1 (en) | 2004-05-04 |
DE10247633A1 (de) | 2004-04-29 |
US7704912B2 (en) | 2010-04-27 |
WO2004035208A1 (de) | 2004-04-29 |
CA2501373C (en) | 2012-12-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4805577B2 (ja) | キラル遷移金属触媒、及び該触媒を用いるキラル有機化合物の接触製造法 | |
van den Berg et al. | Monodentate Phosphoramidites: A Breakthrough in Rhodium‐Catalysed Asymmetric Hydrogenation of Olefins | |
Kamer et al. | Phosphorus (III) ligands in homogeneous catalysis: design and synthesis | |
Brunner | Optically active organometallic compounds of transition elements with chiral metal atoms | |
Nettekoven et al. | Phosphorus-chiral analogues of 1, 1 ‘-bis (diphenylphosphino) ferrocene: asymmetric synthesis and application in highly enantioselective Rhodium-catalyzed hydrogenation reactions | |
JP4754753B2 (ja) | キラルフェロセンホスフィン及び不斉触媒反応におけるその使用 | |
Ayora et al. | Modular approach to new chiral monodentate diamidophosphite ligands. Application in palladium-catalyzed asymmetric hydrovinylation of styrene | |
EP0871621A1 (en) | Asymmetric synthesis catalyzed by transition metal complexes with new chiral ligands | |
Darcel et al. | Direct use of chiral or achiral organophosphorus boranes as pro-ligands for transition metal catalyzed reactions | |
Crochet et al. | Novel ruthenium (II) complexes containing imino-or aminophosphine ligands for catalytic transfer hydrogenation | |
Chuchelkin et al. | Diamidophosphites from β-hydroxyamides: readily assembled ligands for Pd-catalyzed asymmetric allylic substitution | |
Gavrilov et al. | MOP‐Type Binaphthyl Phosphite and Diamidophosphite Ligands and Their Application in Catalytic Asymmetric Transformations | |
CA2380566C (en) | Novel chiral phosphorus ligands and the use thereof in the production of optically active products | |
Colacot et al. | Synthesis, single crystal X-ray structure determination and NMR studies of Cp2Fe (PPh2) 2PtPh2 and Cp2Fe (PPh2) 2PtI2 | |
JP4828773B2 (ja) | 不斉合成のためのリガンドとしてのキラルなモノホスファイト | |
EP2731956B1 (en) | P-chirogenic organophosphorus compounds | |
Hammerer et al. | Synthesis of Binol-based diphosphinites bearing chiral phospholane units and their application in asymmetric catalysis | |
US20040249184A1 (en) | Novel chiral ligands, transition metal complexes thereof, and the catalytic use of the same | |
RU2475492C1 (ru) | Способ получения катионных комплексов палладия с бидентатными фосфорорганическими лигандами | |
Drommi et al. | Rh (I) complexes with new C2‐symmetric chiral diphosphoramidite ligands: Catalytic activity for asymmetric hydrogenation of olefins | |
Pereira et al. | Tervalent phosphorus acid derivatives | |
EP1846350A2 (en) | Improved method for the preparation of enantiomerically enriched secondary alcohols by the addition of organoaluminium reagents to carbonyl compounds | |
Pereira et al. | Tervalent phosphorus acid derivatives | |
CA2346379A1 (en) | Substituted isophosphindolines and their use | |
Junge et al. | Synthesis and catalytic application of novel binaphthyl-derived phosphorous ligands |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060921 |
|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20070928 |
|
RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20080725 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091002 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20091228 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20100108 |
|
A524 | Written submission of copy of amendment under article 19 pct |
Free format text: JAPANESE INTERMEDIATE CODE: A524 Effective date: 20100129 |
|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20101227 Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20101228 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110121 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20110418 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20110425 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20110520 |
|
RD13 | Notification of appointment of power of sub attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7433 Effective date: 20110520 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20110531 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20110523 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110621 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110713 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110811 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140819 Year of fee payment: 3 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |