JP5458303B2 - 光学活性アリールアミノホスホニウム塩、不斉合成反応用触媒、及び光学活性化合物の製造方法 - Google Patents
光学活性アリールアミノホスホニウム塩、不斉合成反応用触媒、及び光学活性化合物の製造方法 Download PDFInfo
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- JP5458303B2 JP5458303B2 JP2009060178A JP2009060178A JP5458303B2 JP 5458303 B2 JP5458303 B2 JP 5458303B2 JP 2009060178 A JP2009060178 A JP 2009060178A JP 2009060178 A JP2009060178 A JP 2009060178A JP 5458303 B2 JP5458303 B2 JP 5458303B2
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- optically active
- salt
- arylaminophosphonium
- present
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- 150000003839 salts Chemical class 0.000 title claims description 77
- 238000006243 chemical reaction Methods 0.000 title claims description 49
- 150000001875 compounds Chemical class 0.000 title claims description 35
- 238000011914 asymmetric synthesis Methods 0.000 title claims description 28
- 239000003054 catalyst Substances 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 43
- 125000001424 substituent group Chemical group 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 150000004982 aromatic amines Chemical class 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- -1 arylamino phosphonium salt Chemical class 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 150000001721 carbon Chemical group 0.000 claims description 8
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 8
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- 125000001769 aryl amino group Chemical group 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 24
- 150000002430 hydrocarbons Chemical group 0.000 description 22
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000013543 active substance Substances 0.000 description 10
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 8
- 239000012038 nucleophile Substances 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- DGFVXRMQRZSKQS-UHFFFAOYSA-N tetraaminophosphanium Chemical class N[P+](N)(N)N DGFVXRMQRZSKQS-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000005018 aryl alkenyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000005015 aryl alkynyl group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
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- 238000010898 silica gel chromatography Methods 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
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- FBUMZWZXFBZQAH-WJOKGBTCSA-N C1(=CC=CC=C1)[C@]1(C(C(=C2C=CC=CC2=C1)C1=C(C(=CC2=CC=CC=C12)C1=CC=CC=C1)N)(N)N)N Chemical compound C1(=CC=CC=C1)[C@]1(C(C(=C2C=CC=CC2=C1)C1=C(C(=CC2=CC=CC=C12)C1=CC=CC=C1)N)(N)N)N FBUMZWZXFBZQAH-WJOKGBTCSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002635 aromatic organic solvent Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 238000004296 chiral HPLC Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000006574 non-aromatic ring group Chemical group 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 0 *c(c(*)c1*)c(*)c(-c2c(*)c(*)c(*)c(*)c2N2)c1NP21Nc2c(*)c(*)c(*)c(*)c2-c(c(*)c(*)c(*)c2*)c2N1 Chemical compound *c(c(*)c1*)c(*)c(-c2c(*)c(*)c(*)c(*)c2N2)c1NP21Nc2c(*)c(*)c(*)c(*)c2-c(c(*)c(*)c(*)c2*)c2N1 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DDAPSNKEOHDLKB-UHFFFAOYSA-N 1-(2-aminonaphthalen-1-yl)naphthalen-2-amine Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3N)=C(N)C=CC2=C1 DDAPSNKEOHDLKB-UHFFFAOYSA-N 0.000 description 1
- ZAPYLSLVQJQGEY-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-amine Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3N)=CC=CC2=C1 ZAPYLSLVQJQGEY-UHFFFAOYSA-N 0.000 description 1
- OHJTUNNQJBGHHJ-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene-2,3-diamine Chemical class C1=CC=C2C(C=3C4=CC=CC=C4C=C(C=3N)N)=CC=CC2=C1 OHJTUNNQJBGHHJ-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- GEQNZVKIDIPGCO-UHFFFAOYSA-N 2,4-dimethoxyaniline Chemical compound COC1=CC=C(N)C(OC)=C1 GEQNZVKIDIPGCO-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- KIPMDPDAFINLIV-UHFFFAOYSA-N 2-nitroethanol Chemical compound OCC[N+]([O-])=O KIPMDPDAFINLIV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004361 3,4,5-trifluorophenyl group Chemical group [H]C1=C(F)C(F)=C(F)C([H])=C1* 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- WHCIRKFRQZNUDG-KRWDZBQOSA-N NC1(C(=C2C=CC=CC2=C[C@@H]1N)C1=C(C=CC2=CC=CC=C12)N)N Chemical compound NC1(C(=C2C=CC=CC2=C[C@@H]1N)C1=C(C=CC2=CC=CC=C12)N)N WHCIRKFRQZNUDG-KRWDZBQOSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
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- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005966 aza-Michael addition reaction Methods 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
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- 238000005859 coupling reaction Methods 0.000 description 1
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- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
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- 238000003818 flash chromatography Methods 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
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- 238000002329 infrared spectrum Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PIAOLBVUVDXHHL-VOTSOKGWSA-N β-nitrostyrene Chemical compound [O-][N+](=O)\C=C\C1=CC=CC=C1 PIAOLBVUVDXHHL-VOTSOKGWSA-N 0.000 description 1
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
また、本発明の光学活性アリールアミノホスホニウム塩(以下、「本発明の塩」ともいう。)は、下記式(1−2)又は(1−3)で表される。式(1−2)及び(1−3)中、R 1 及びR 8 は、それぞれ独立に、水素原子、炭素数1〜8のアルキル基又は炭素数4〜15のアリール基であり、該アリール基は、ハロゲン原子及びアルキル基から選ばれる置換基を1〜3個有していてもよい。R 2 、R 7 、R 9 、R 10 、R 15 及びR 16 は、それぞれ独立に、水素原子又は炭素数1〜8のアルキル基である。X − は対イオンである。
式(1)中、R1〜R16は、それぞれ独立に水素原子又は任意の置換基である。該任意の置換基の種類には特に限定はない。上記任意の置換基は、炭化水素基を有する置換基でもよく、炭化水素基を有しない置換基でもよい。
本発明の触媒は、本発明の塩を含む限り、その組成には特に限定はない。本発明の触媒は、本発明の塩のみからなる構成でもよく、他の成分を含んでいてもよい。
本発明の製造方法では、本発明の塩の存在下、 電子吸引性基により活性化された炭素−炭素不飽和結合(二重結合又は三重結合)への求核付加反応を行い、光学活性化合物を製造する。
光学活性アリールアミノホスホニウム塩の合成経路を以下に示す。
〔1〕1H−NMR(500MHz,CD3OD);δ8.021(2H,s),8.017(2H,d,J=8.5Hz),7.96(2H,d,J=8.5Hz),7.90(2H,d,J=8.5Hz),7.51−7.47(8H,m),7.40 (2H,d,J=8.5Hz),7.25(2H,t,J=8.5Hz),7.23(2H,t,J=8.5Hz),6.99(2H,d,J=8.5Hz),6.97(2H,d,J=8.5Hz),6.91−6.86(6H,m),N−H protons were not found due to deuteration.
〔2〕13C−NMR(126MHz,CD3OD);δ139.0,138.4(d,JP−C=3.7Hz),136.8(d,JP−C=6.3Hz),134.13(d,JP−C=1.4Hz),134.09(d,JP−C=1.4Hz),133.6(d,JP−C=1.4Hz),133.2(d,JP−C=1.4Hz),133.1(d,JP−C=5.9Hz),132.0,131.3,130.6(d,JP−C=1.9Hz),130.5,129.4,129.2,128.6,128.43,128.40,127.7,127.6,127.4,127.2 (d,JP−C=2.4Hz),126.7,124.2(d,JP−C=3.7Hz),one carbon was not found probably due to overlapping.
〔3〕31P−NMR(121MHz,CD3OD);δ46.9
〔1〕1H−NMR(500MHz,アセトン−d6);δ8.13(2H,d,J=8.5Hz),8.05(2H,s),8.04(2H,d,J=8.5Hz),7.97(2H,d,J=8.5Hz),7.80(8H,brs),7.68(4H,brs),7.60(2H,t,J=8.5Hz),7.56(2H,t,J=8.5Hz),7.44(4H,d,J=7.5Hz),7.35(2H,t,J=8.5Hz),7.32(2H,t,J=8.5Hz),7.30(2H,d,J=8.5Hz),7.05(2H,d,J=8.5Hz),7.00(2H,d,J=8.5Hz),6.89(4H,t,J=7.5Hz),6.84(2H,t,J=7.5Hz),N−H protons were not found due to broadening.
〔2〕13C−NMR(126MHz,アセトン−d6):δ162.6(q,JB−C=50.0Hz),138.4,138.0(d,JP−C=3.2Hz),136.1(d,JP−C=5.9Hz),135.6,133.7,133.0,132.79(d,JP−C=8.2Hz),132.76,131.8,131.2,130.11,130.09(d,JP−C=5.9Hz),130.03(q,JF−C=31.6Hz),129.4,129.3,129.0,128.4,128.2,128.1,127.7,127.6,127.4,126.6,125.4(q,JF−C=272.5Hz),124.4(d,JP−C=4.2Hz),118.5,two carbons were not found probably due to overlapping.
〔3〕19F−NMR(282MHz,アセトン−d6):δ−62.6
〔4〕31P−NMR(121MHz,アセトン−d6):δ45.4
〔5〕IR(KBr):3373,3065,1610,1500,1415,1356,1278,1128,993,887,752,712cm−1
〔6〕HRMS(ESI−TOF);Calcd for C52H36N4P+([M]+)747.2672,Found 747.2694
〔7〕[α]D 24;16.4°(c=0.21,CHCl3)
3,3’−ジフェニル−(R)−2,2’−ジアミノ−1,1’−ビナフチルジアミンに代えて、種々の3,3’−ジアリール置換ビナフチルジアミンを用い、上記合成(I)と同様の手順により、以下に示すアリールアミノホスホニウム塩(1a・Cl)、(1a・BArF)、(1b・Cl)、(1b・BArF)、(2c・Cl)、及び(2c・BArF)を得た。(1a・BArF)、(1b・BArF)、及び(2c・BArF)これらの1H−NMR及び13C−NMRのスペクトルを図2〜図4に示す。スペクトルデータは以下の通りである。
〔1〕1H−NMR(500MHz,CD3OD);δ8.18(4H,d,J=8.5Hz),8.03(4H,d,J=8.5Hz),7.57(4H,d,J=8.5Hz),7.48(4H,t,J=8.5Hz),7.24(4H,t,J=8.5Hz),7.07(4H,d,J=8.5Hz),N−H protons were not found due to deuteration.
〔2〕13C−NMR(126MHz,CD3OD):δ135.7(d,JP−C=5.0Hz),134.2(d,JP−C=1.4Hz),133.4(d,JP−C=1.4Hz),131.5,129.4,128.24,128.16(d,JP−C=2.3Hz),127.7,126.8,125.0(d,JP−C=3.3Hz)
〔4〕31P−NMR(121MHz,CD3OD):δ50.2
〔1〕1H−NMR(500MHz,アセトン−d6);δ8.27(4H,d,J=8.5Hz),8.14(4H,d,J=8.5Hz),7.79(8H,brs),7.77(4H,d,J=8.5Hz),7.68(4H,brs),7.58(4H,t,J=8.5Hz),7.36(4H,t,J=8.5Hz),7.16(4H,d,J=8.5Hz),N−H protons were not found due to broadening.
〔2〕13C−NMR(126MHz,アセトン−d6):
δ162.6(q,JB−C=50.0Hz),135.5,134.9(d,JP−C=5.0Hz),133.6,133.0,131.5,130.0(q,JF−C=31.8Hz),129.4,127.93,127.86,127.5(d,JP−C=2.3Hz),126.9,125.4(q,JF−C=272.5Hz),124.9(d,JP−C=3.3Hz),118.5
〔3〕19F−NMR(282MHz,アセトン−d6):δ−62.6
〔4〕31P−NMR(121MHz,アセトン−d6):δ50.7
〔5〕IR(KBr):3386,3059,1508,1356,1279,1126,988,814,757,713cm−1
〔6〕HRMS(ESI−TOF);Calcd for C40H28N4P+([M]+)595.2046.Found 595.2073
〔7〕[α]D 22;−2.6°(c=0.57,CHCl3)
〔1〕1H−NMR(500MHz,CD3OD);δ8.19(2H,s),8.08(2H,d,J=8.0Hz),7.90(2H,d,J=8.0Hz),7.82(2H,d,J=8.0Hz),7.73(4H,dt,J=7.5,1.5Hz),7.52(2H,t,J=8.0Hz),7.45(4H,tt,J=7.5,1.5Hz),7.39(2H,tt,J=7.5,1.5Hz),7.38(2H,t,J=7.5Hz),7.26(2H,td,J=8.0,1.5Hz),7.11(2H,d,J=8.0Hz),7.08(2H,td,J=8.0,1.5Hz),6.99(2H,d,J=8.0Hz),6.76(2H,d,J=8.0Hz),N−H protons were not found due to deuteration.
〔2〕13C−NMR(126MHz,CD3OD);δ139.3,138.3(d,JP−C=3.2Hz),134.4(d,JP−C=5.0Hz),134.1,133.9(d,JP−C=1.4Hz),133.5,132.9(d,JP−C=1.4Hz),132.5,131.9(d,JP−C=3.7Hz),131.0,130.9,130.7(d,JP−C=2.3Hz),130.2,129.4,129.3,129.2,128.3,128.1,128.0,127.5,127.4,127.2(d,JP−C=2.3Hz),126.6,125.0(d,JP−C=3.8Hz)
〔3〕31P−NMR(121MHz,CD3OD);δ44.3
〔1〕1H−NMR(500MHz,アセトン−d6);δ8.20(2H,s),8.18(2H,d,J=8.5Hz),7.98(2H,d,J=8.5Hz),7.95(2H,d,J=8.5Hz),7.79(8H,brs),7.70−7.63(8H,m),7.62(2H,t,J=8.5Hz),7.452(2H,d,J=8.5Hz),7.449(2H,t,J=8.5Hz),7.41(4H,t,J=8.5Hz),7.37(2H,d,J=8.5Hz),7.36(2H,t,J=8.5Hz),7.18(2H,t,J=8.5Hz),7.05(2H,d,J=8.5Hz),6.86(2H,d,J=8.5Hz),N−H protons were not found due to broadening.
〔2〕13C−NMR(126MHz,アセトン−d6);δ162.6(q,JB−C=50.0Hz),138.7,138.1(d,JP−C=3.2Hz),135.5,134.4(d,JP−C=5.5Hz),133.7,133.4,132.8,132.4(d,JP−C=1.8Hz),132.2,130.9,130.0(q,JF−C=31.6Hz),129.9(d,JP−C=2.8Hz),129.7,129.2,129.1,128.9,128.1,127.8,127.7,127.33,127.29,126.4,126.2(d,JP−C=2.4Hz),125.4(q,JF−C=273.0Hz),124.9,118.5, two carbons were not found probably due to overlapping.
〔3〕19F−NMR(282MHz,アセトン−d6);δ−62.6
〔4〕31P−NMR(121MHz,アセトン−d6);δ45.1
〔5〕IR(KBr);3348,3064,1703,1610,1508,1419,1356,1279,1126,989,887,751,713cm−1
〔6〕HRMS(ESI−TOF);Calcd for C52H36N4P+([M]+)747.2672.Found 747.2688
〔7〕[α]D 23;−40.0°(c=0.50,CHCl3)
〔1〕1H−NMR(500MHz,CD3OD);δ8.09(2H,s),8.07(2H,d,J=8.5Hz),7.96(2H,d,J=8.5Hz),7.95(2H,d,J=8.5Hz),7.54(2H,t,J=8.5Hz),7.46(2H,t,J=8.5Hz),7.41(2H,t,J=8.5Hz),7.33−7.25(6H,m),7.20(2H,t,J=8.5Hz),7.01(2H,d,J=8.5Hz),6.90(2H,d,J=8.5Hz),N−H protons were not found due to deuteration.
〔2〕13C−NMR(126MHz,CD3OD);δ151.7(ddd,JF−C=249.2,10.0,3.8Hz),140.3(dt,JF−C=252.3,15.2Hz),136.7(d,JP−C=6.0Hz),136.3,135.7(td,JF−C=9.2,4.5Hz),134.4,133.8,133.6,132.9,132.6,132.5(d,JP−C=3.9Hz),131.8,131.2,129.7,129.3,128.4,128.3,128.1,127.8,127.5,126.9(d,JP−C=1.0Hz),126.7,124.2(d,JP−C=3.8Hz),115.4(dd,JF−C=16.9,4.5Hz)
〔3〕19F−NMR(282MHz,CD3OD):δ−136.7(dd,J=18.9,8.7Hz),−163.8(tt,J=20.6,6.8Hz)
〔4〕31P−NMR(121MHz,CD3OD);δ46.4
〔1〕1H−NMR(500MHz,アセトン−d6);δ8.15(2H,d,J=8.5Hz),8.14(2H,s),8.01(2H,d,J=8.5Hz),8.00(2H,d,J=8.5Hz),7.79(8H,brs),7.68(4H,brs),7.63(2H,t,J=8.5Hz),7.51(2H,t,J=8.5Hz),7.40(2H,t,J=8.5Hz),7.33−7.24(8H,m),7.09(2H,d,J=8.5Hz),6.91(2H,d,J=8.5Hz),N−H protons were not found due to broadening.
〔2〕13C−NMR(126MHz,アセトン−d6);
δ162.6(q,JB−C=50.0Hz),151.1(ddd,JF−C=249.1,9.6,3.7Hz),139.6(dt,JF−C=251.9,2.8Hz),136.0,135.8,135.5,135.4,134.0,133.4,132.8,132.4,132.2,131.1,130.0(q,JF−C=31.6Hz),129.6,129.2,128.3,128.2,127.7,127.6,126.7,126.6,125.4(q,JF−C=272.4Hz),124.4(d,JP−C=4.2Hz),118.5,115.2(dd,JF−C=17.0,5.0Hz),three carbons were not found probably due to overlapping.
〔3〕19F−NMR(282MHz,アセトン−d6);δ−62.6,−135.7,−162.3
〔4〕31P−NMR(121MHz,アセトン−d6);δ44.5
〔5〕IR(KBr);3381,3064,1615,1530,1420,1356,1280,1127,1050,752cm−1
〔6〕HRMS(ESI−TOF);Calcd for C52H30F6N4P+([M]+)855.2107.Found 855.5109
〔7〕[α]D 24;10.5°(c=0.25,CHCl3)
ニトロオレフィン(2)として、ニトロスチレンを用いた。芳香族アミンとして表1に示すアリール基(Ar1)を持つアニリン誘導体を用いた。以下の方法により、β−アミノニトロアルカンを合成した。
ニトロオレフィン(2)として、表2に示す一価の炭化水素基(R)を持つニトロオレフィンを用いた。芳香族アミンとして、2,4−ジメトキシアニリンを用い、テトラアミノホスホニウム塩として、上記「2c・BArF」を用いた。これらを用いて、上記と同様の方法により、β−アミノニトロアルカンを合成した。但し、反応時間は基質であるニトロオレフィン(2)に応じて変更している(表2に記載)。そして、得られたβ−アミノニトロアルカンの収率及び鏡像過剰率を測定した。その結果を表2に示す。鏡像過剰率の測定方法は上記の通りである。
Claims (12)
- R1及びR8が、それぞれ独立に、水素原子、炭素数4〜15のアリール基又はハロゲン原子の置換基を有する炭素数4〜15のアリール基である請求項1に記載の光学活性アリールアミノホスホニウム塩。
- R 1 及びR 8 が、それぞれ独立に、水素原子、フェニル基又はハロゲン化フェニル基である請求項1又は2に記載の光学活性アリールアミノホスホニウム塩。
- R 2 、R 7 、R 9 、R 10 、R 15 及びR 16 は、それぞれ独立に、水素原子又は炭素数1〜3のアルキル基である請求項2又は3に記載の光学活性アリールアミノホスホニウム塩。
- X−はテトラアリールホウ酸イオンである請求項1乃至4のいずれかに記載の光学活性アリールアミノホスホニウム塩。
- 請求項1乃至5のいずれかに記載の光学活性アリールアミノホスホニウム塩を含む不斉合成反応用触媒。
- 上記不斉合成反応は、電子吸引性基により活性化された炭素−炭素不飽和結合への求核付加反応である請求項6記載の不斉合成反応用触媒。
- 上記不斉合成反応は、ニトロオレフィン類及び芳香族アミンを反応させるβ−アミノニトロアルカンの合成反応である請求項6又は7記載の不斉合成反応用触媒。
- 請求項1乃至5のいずれかに記載の光学活性アリールアミノホスホニウム塩の存在下、電子吸引性基により活性化された炭素−炭素不飽和結合への求核付加反応を行い、光学活性化合物を製造する方法。
- 式(2)で表される化合物がニトロオレフィン類である請求項10記載の光学活性化合物を製造する方法。
- 上記芳香族アミンが、芳香環に電子供与性基を有する芳香族アミンである請求項10又は11記載の光学活性化合物を製造する方法。
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