JPH09208566A - Optically active oxazoline compound and asymmetric allyl oxidization reaction - Google Patents
Optically active oxazoline compound and asymmetric allyl oxidization reactionInfo
- Publication number
- JPH09208566A JPH09208566A JP1868296A JP1868296A JPH09208566A JP H09208566 A JPH09208566 A JP H09208566A JP 1868296 A JP1868296 A JP 1868296A JP 1868296 A JP1868296 A JP 1868296A JP H09208566 A JPH09208566 A JP H09208566A
- Authority
- JP
- Japan
- Prior art keywords
- group
- optically active
- trisoxazoline
- formula
- copper complex
- 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.)
- Pending
Links
- -1 oxazoline compound Chemical class 0.000 title claims abstract description 67
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 23
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title abstract description 6
- 108010033522 westiellamide Proteins 0.000 claims abstract description 51
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 150000004699 copper complex Chemical class 0.000 claims abstract description 8
- MIDTUAMKJJDHAR-YAWPOEEYSA-N Westiellamide Chemical compound N([C@@H]([C@H](O1)C)C(=O)N[C@H](C2=N[C@@H]([C@H](O2)C)C(=O)N[C@H]2C(C)C)C(C)C)=C1[C@H](C(C)C)NC(=O)[C@@H]1[C@@H](C)OC2=N1 MIDTUAMKJJDHAR-YAWPOEEYSA-N 0.000 claims abstract description 6
- 125000000746 allylic group Chemical group 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 13
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 5
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002976 peresters Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000010949 copper Substances 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 abstract description 2
- YQOCHIIDVCLPOS-UHFFFAOYSA-N 2-[carboxymethyl-(2-methoxy-2-oxoethyl)amino]acetic acid Chemical compound COC(=O)CN(CC(O)=O)CC(O)=O YQOCHIIDVCLPOS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 150000001925 cycloalkenes Chemical class 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- QTYIIXIGTKZSSR-UHFFFAOYSA-N n,n-diethylethanamine;tetrachloromethane;triphenylphosphane Chemical compound ClC(Cl)(Cl)Cl.CCN(CC)CC.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QTYIIXIGTKZSSR-UHFFFAOYSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 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 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 3
- HWUPLUNLNUHIQZ-UHFFFAOYSA-N copper;trifluoromethanesulfonic acid Chemical compound [Cu].OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F HWUPLUNLNUHIQZ-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJXJGQCXFSSHNL-MRVPVSSYSA-N (2s)-2-amino-2-phenylethanol Chemical compound OC[C@@H](N)C1=CC=CC=C1 IJXJGQCXFSSHNL-MRVPVSSYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 229940076286 cupric acetate Drugs 0.000 description 2
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 2
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- VGLKHVQPWGFXEG-NCJHBDPTSA-K europium(3+);(1z)-2,2,3,3,4,4,4-heptafluoro-1-(4,7,7-trimethyl-3-oxo-2-bicyclo[2.2.1]heptanylidene)butan-1-olate Chemical compound [Eu+3].C1CC2(C)C(=O)\C(=C(/[O-])C(F)(F)C(F)(F)C(F)(F)F)C1C2(C)C.C1CC2(C)C(=O)\C(=C(/[O-])C(F)(F)C(F)(F)C(F)(F)F)C1C2(C)C.C1CC2(C)C(=O)\C(=C(/[O-])C(F)(F)C(F)(F)C(F)(F)F)C1C2(C)C VGLKHVQPWGFXEG-NCJHBDPTSA-K 0.000 description 2
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 125000005484 neopentoxy group Chemical group 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000005920 sec-butoxy group Chemical group 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- CBIBNYRWDKSIMD-UHFFFAOYSA-N 2,2,4,4-tetramethylhexaneperoxoic acid Chemical compound CCC(C)(C)CC(C)(C)C(=O)OO CBIBNYRWDKSIMD-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- MWSMQQDRVGPSSW-UHFFFAOYSA-N 3-tert-butylperoxy-2,2-dimethylpropanoic acid Chemical compound CC(C)(C)OOCC(C)(C)C(O)=O MWSMQQDRVGPSSW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BTLKCQKGDWHFJF-LLVKDONJSA-N [(1s)-cyclopent-2-en-1-yl] benzoate Chemical compound C=1C=CC=CC=1C(=O)O[C@H]1CCC=C1 BTLKCQKGDWHFJF-LLVKDONJSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940125810 compound 20 Drugs 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- RUBFCLDQBHUROT-WCCKRBBISA-N copper;(2s)-pyrrolidine-2-carboxylic acid Chemical compound [Cu].OC(=O)[C@@H]1CCCN1 RUBFCLDQBHUROT-WCCKRBBISA-N 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- NWYYWIJOWOLJNR-RXMQYKEDSA-N l-valinol Chemical compound CC(C)[C@H](N)CO NWYYWIJOWOLJNR-RXMQYKEDSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- NHKRXCTYPGGSTL-UHFFFAOYSA-N methyl 2-[bis(2-methoxy-2-oxoethyl)amino]acetate Chemical compound COC(=O)CN(CC(=O)OC)CC(=O)OC NHKRXCTYPGGSTL-UHFFFAOYSA-N 0.000 description 1
- FMHCTGIUWVNBFI-UHFFFAOYSA-N n,n-diethylethanamine;tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl.CCN(CC)CC FMHCTGIUWVNBFI-UHFFFAOYSA-N 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000002825 nitriles Chemical class 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
- 239000012044 organic layer Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- BBXFLQCFPROIMX-UHFFFAOYSA-N tert-butyl propaneperoxoate Chemical compound CCC(=O)OOC(C)(C)C BBXFLQCFPROIMX-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は光学活性トリスオキ
サゾリン化合物に関し、更に光学活性トリスオキサゾリ
ン化合物を配位子とする銅錯体及び／又は光学活性トリ
スオキサゾリン銅錯体を使用することを特徴とする不斉
アリル酸化反応に関するものである。TECHNICAL FIELD The present invention relates to an optically active trisoxazoline compound, and further, an asymmetry characterized by using a copper complex having an optically active trisoxazoline compound as a ligand and / or an optically active trisoxazoline copper complex. It relates to the allyl oxidation reaction.
【０００２】[0002]
【従来の技術】不斉アリル酸化反応は、プロキラルなオ
レフィンから医薬、農薬を始めとする種々のファインケ
ミカルの重要な中間体である光学活性アリルアルコール
を合成する有用な製造方法である。不斉アリル酸化反応
としては、光学活性遷移金属錯体を触媒として用いる反
応が知られており、例えば、Tetrahedron Letters 36,
1831 (1995) 、Tetrahedron Letters 36, 2495 (1995)
には、光学活性ビスオキサゾリン銅錯体を用いた反応
が、Tetrahedron : Asymmetry 6, 147 (1995) 及び Tet
rahedron :Asymmetry 6, 661 (1995) には、光学活性プ
ロリン銅錯体を用いた反応が報告されている。The asymmetric allylic oxidation reaction is a useful production method for synthesizing optically active allyl alcohol, which is an important intermediate for various fine chemicals such as pharmaceuticals and agricultural chemicals, from prochiral olefins. As the asymmetric allylic oxidation reaction, a reaction using an optically active transition metal complex as a catalyst is known, and for example, Tetrahedron Letters 36 ,
1831 (1995), Tetrahedron Letters 36 , 2495 (1995)
, Tetrahedron: Asymmetry 6 , 147 (1995) and Tetrahedron: Asymmetry 6 ,
In rahedron: Asymmetry 6 , 661 (1995), a reaction using an optically active proline copper complex has been reported.
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記の不斉ア
リル酸化反応において触媒として用いられる光学活性金
属錯体は現在も種々の改良がなされており、触媒性能及
び経済性を考慮した更に優れた触媒の開発研究が盛んに
行なわれているのが現状である。However, various improvements have been made to the optically active metal complexes used as catalysts in the above-mentioned asymmetric allylic oxidation reaction, and further excellent catalysts in consideration of catalytic performance and economic efficiency have been made. The current situation is that development research is being actively conducted.
【０００４】[0004]
【課題を解決するための手段】本発明者は、不斉アリル
酸化反応について鋭意検討を重ねた結果、光学活性トリ
スオキサゾリン化合物を開発し、光学活性トリスオキサ
ゾリン化合物を配位子とする銅錯体が不斉アリル酸化反
応の触媒として極めて有用であることを見出し、本発明
を完成するに至った。Means for Solving the Problems As a result of extensive studies on the asymmetric allylic oxidation reaction, the present inventor has developed an optically active trisoxazoline compound, and found that a copper complex having an optically active trisoxazoline compound as a ligand They have found that they are extremely useful as catalysts for asymmetric allylic oxidation reactions, and have completed the present invention.
【０００５】即ち、本発明は、式（１）That is, the present invention provides the following formula (1)
【０００６】[0006]
【化８】 Embedded image
【０００７】又は式（２）Or equation (2)
【０００８】[0008]
【化９】 Embedded image
【０００９】〔式中、Ｒ1及びＲ2はそれぞれ独立して、
Ｃ1〜6アルキル基、フェニル基（該フェニル基は、ハロ
ゲン原子、Ｃ1〜6アルキル基、Ｃ1〜6アルコキシ基で置
換されていてもよい。）、ベンジル基（該ベンジル基
は、ハロゲン原子、Ｃ1〜6アルキル基、Ｃ1〜6アルコキ
シ基で置換されていてもよい。）を示す。ｎは１〜３の
整数を示す。＊は不斉炭素原子を示し、その炭素原子の
絶対配置はＲかＳを意味する。〕で表わされる光学活性
トリスオキサゾリン化合物、式（３）[In the formula, R 1 and R 2 are each independently
C 1 ~ 6 alkyl group, a phenyl group (the phenyl group, a halogen atom, C 1 ~ 6 alkyl group, optionally substituted with C 1 ~ 6 alkoxy group.), Benzyl group (said benzyl group are halogen atom, C 1 ~ 6 alkyl group, optionally substituted with C 1 ~ 6 alkoxy group. the) shows. n shows the integer of 1-3. * Indicates an asymmetric carbon atom, and the absolute configuration of the carbon atom means R or S. ] An optically active trisoxazoline compound represented by the formula (3)
【００１０】[0010]
【化１０】 Embedded image
【００１１】又は式（４）Or equation (4)
【００１２】[0012]
【化１１】 Embedded image
【００１３】〔式中、 Ｘは、アセトキシ基、トリフル
オロメタンスルホニル基、シアノ基、ハロゲン原子を示
す。ｍは１又は２の整数を示す。Ｒ1、Ｒ2、ｎ及び＊は
前記に同じ。〕で表わされる光学活性トリスオキサゾリ
ン銅錯体及び、式（５）[In the formula, X represents an acetoxy group, a trifluoromethanesulfonyl group, a cyano group, or a halogen atom. m represents an integer of 1 or 2. R 1 , R 2 , n and * are the same as above. ] An optically active trisoxazoline copper complex represented by the formula:
【００１４】[0014]
【化１２】 Embedded image
【００１５】〔式中、ｒは１〜４の整数を意味する。〕
で表わされる環状オレフィンと、式（６）[In the formula, r means an integer of 1 to 4. ]
And a cyclic olefin represented by the formula (6)
【００１６】[0016]
【化１３】 Embedded image
【００１７】〔式中、Ｗは、Ｃ1〜8アルキル基、フェニ
ル基（該フェニル基は、ハロゲン原子、Ｃ1〜6アルキル
基、Ｃ1〜6アルコキシ基で置換されていてもよい。）を
示す。Ｚは、水素原子又はＣ1〜8アルキル基を示す。〕
で表わされる過酸エステルを、式（１）及び／又は式
（２）の光学活性トリスオキサゾリン化合物を配位子と
する銅錯体、及び／又は（３）及び／又は式（４）の光
学活性トリスオキサゾリン銅錯体の存在下、反応させ
て、式（７）[0017] wherein, W is, C 1 ~ 8 alkyl group, a phenyl group (the phenyl group, a halogen atom, C 1 ~ 6 alkyl group, optionally substituted with C 1 ~ 6 alkoxy group.) Indicates. Z represents a hydrogen atom or a C 1 ~ 8 alkyl group. ]
A copper complex having an optically active trisoxazoline compound of formula (1) and / or formula (2) as a ligand, and / or (3) and / or an optical activity of formula (4) By reacting in the presence of a trisoxazoline copper complex, the compound of formula (7)
【００１８】[0018]
【化１４】 Embedded image
【００１９】〔式中、Ｗ、ｒ及び＊は前記に同じ。〕で
表わされる光学活性アリルアルコールを得ることを特徴
とするオレフィンの不斉アリル酸化反応に関するもので
ある。[In the formula, W, r and * are the same as defined above. ] It is related with the asymmetric allyl oxidation reaction of the olefin characterized by obtaining the optically active allyl alcohol represented by these.
【００２０】[0020]
【発明の実施の形態】置換基Ｒ1、Ｒ2、Ｗ及びＺについ
て説明する。ハロゲン原子としては、フッソ原子、塩素
原子、臭素原子、沃素原子等が挙げられる。Ｃ1〜6アル
キル基としては、メチル基、エチル基、ｎ−プロピル
基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓ
ｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−アミル基、
ｉ−アミル基、ネオペンチル基、ヘキシル基、シクロヘ
キシル基等が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The substituents R 1 , R 2 , W and Z will be described. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. The C 1 ~ 6 alkyl group, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, s
ec-butyl group, tert-butyl group, n-amyl group,
Examples thereof include i-amyl group, neopentyl group, hexyl group and cyclohexyl group.
【００２１】Ｃ1〜8アルキル基としては、メチル基、エ
チル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル
基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチ
ル基、ｎ−アミル基、ｉ−アミル基、ネオペンチル基、
ヘキシル基、ヘプチル基、オクチル基、２−エチルヘキ
シル基、シクロヘキシル基等が挙げられる。ハロゲン原
子、Ｃ1〜6アルキル基、Ｃ1〜6アルコキシ基で置換され
ていてもよいフェニル基としては、フッソ原子、塩素原
子、臭素原子、沃素原子、メチル基、エチル基、ｎ−プ
ロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル
基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−アミ
ル基、ｉ−アミル基、ネオペンチル基、ヘキシル基、シ
クロヘキシル基、メトキシ基、エトキシ基、ｎ−プロポ
キシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、ｉ−ブト
キシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、
ｎ−アミロキシ基、ｉ−アミロキシ基、ネオペンチルオ
キシ基、ヘキシルオキシ基、シクロヘキシルオキシ基よ
り選ばれる１個以上の置換基によって置換されていても
よいフェニル基等が挙げられる。Examples of the C 1 ~ 8 alkyl group, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl group, sec- butyl group, tert- butyl group, n- Amyl group, i-amyl group, neopentyl group,
Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, cyclohexyl group and the like can be mentioned. The halogen atom, C 1 ~ 6 alkyl group, a phenyl group which may be substituted with C 1 ~ 6 alkoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n- propyl group , I-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-amyl group, i-amyl group, neopentyl group, hexyl group, cyclohexyl group, methoxy group, ethoxy group , N-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, tert-butoxy group,
Examples thereof include a phenyl group which may be substituted with one or more substituents selected from an n-amyloxy group, an i-amyloxy group, a neopentyloxy group, a hexyloxy group and a cyclohexyloxy group.
【００２２】ハロゲン原子、Ｃ1〜6アルキル基、Ｃ1〜6
アルコキシ基で置換されていてもよいベンジル基として
は、フッソ原子、塩素原子、臭素原子、沃素原子、メチ
ル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ
−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒ
ｔ−ブチル基、ｎ−アミル基、ｉ−アミル基、ネオペン
チル基、ヘキシル基、シクロヘキシル基、メトキシ基、
エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ
−ブトキシ基、ｉ−ブトキシ基、ｓｅｃ−ブトキシ基、
ｔｅｒｔ−ブトキシ基、ｎ−アミロキシ基、ｉ−アミロ
キシ基、ネオペンチルオキシ基、ヘキシルオキシ基、シ
クロヘキシルオキシ基の中から選ばれる１個以上の置換
基によって置換されていてもよいベンジル基等が挙げら
れる。The halogen atom, C 1 ~ 6 alkyl group, C 1 ~ 6
Examples of the benzyl group which may be substituted with an alkoxy group include a fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, i-propyl group, n
-Butyl group, i-butyl group, sec-butyl group, ter
t-butyl group, n-amyl group, i-amyl group, neopentyl group, hexyl group, cyclohexyl group, methoxy group,
Ethoxy group, n-propoxy group, i-propoxy group, n
-Butoxy group, i-butoxy group, sec-butoxy group,
and a benzyl group which may be substituted with one or more substituents selected from tert-butoxy group, n-amyloxy group, i-amyloxy group, neopentyloxy group, hexyloxy group and cyclohexyloxy group. To be
【００２３】置換基Ｒ1及びＲ2の好ましい例としては、
メチル基、エチル基、ｉ−プロピル基、ｔｅｒｔ−ブチ
ル基、フェニル基等が挙げられる。光学活性トリスオキ
サゾリン化合物の合成法について代表例を挙げて説明す
る。スキーム１に、式（２）の光学活性トリスオキサゾ
リン化合物〔ｎ＝１、Ｒ1は前記に同じ。〕の合成例を
示す。Preferred examples of the substituents R 1 and R 2 are:
Examples thereof include a methyl group, an ethyl group, an i-propyl group, a tert-butyl group and a phenyl group. A method for synthesizing the optically active trisoxazoline compound will be described with reference to typical examples. In Scheme 1, an optically active trisoxazoline compound of the formula (2) [n = 1, R 1 is the same as above. ] The example of synthesis of is shown.
【００２４】ニトリロ三酢酸を、（ａ）フィッシャーの
エステル化によりメチルエステル化しニトリロ三酢酸メ
チルエステルとし、（ｂ）光学活性アミノエタノールと
反応させβ−ヒドロキシアミドとし、（ｃ）トリフェニ
ルホスフィン−四塩化炭素−トリエチルアミン系で環化
させて光学活性トリスオキサゾリン化合物を合成する。Nitrilotriacetic acid is methyl esterified by (a) Fischer's esterification to form nitrilotriacetic acid methyl ester, (b) reacted with optically active aminoethanol to give β-hydroxyamide, and (c) triphenylphosphine-4. An optically active trisoxazoline compound is synthesized by cyclizing with a carbon chloride-triethylamine system.
【００２５】[0025]
【化１５】 Embedded image
【００２６】〔式中、ＰＰｈ3はトリフェニルホスフィ
ン、ＴＥＡはトリエチルアミンを示す。Ｒ2及び＊は前
記に同じ。〕 同様に、式（１）の光学活性トリスオキサゾリン化合物
も合成することができる。次に、光学活性トリスオキサ
ゾリン銅錯体の合成法について代表例を挙げて説明す
る。[In the formula, PPh 3 represents triphenylphosphine, and TEA represents triethylamine. R 2 and * are the same as above. Similarly, the optically active trisoxazoline compound of the formula (1) can also be synthesized. Next, a method for synthesizing the optically active trisoxazoline copper complex will be described with reference to representative examples.
【００２７】スキーム２に、式（４）の光学活性トリス
オキサゾリン銅錯体〔Ｘ＝ＯＳＯ2ＣＦ3、ｎ＝１、ｍ＝
２、Ｒ1及び＊は前記に同じ。〕の合成例を示す。即
ち、スキーム１で得られた光学活性トリスオキサゾリン
化合物を窒素雰囲気下、トリフルオロメタンスルホン酸
銅（II）と反応させ、光学活性トリスオキサゾリン銅錯
体を合成する。In Scheme 2, the optically active trisoxazoline copper complex of the formula (4) [X = OSO 2 CF 3 , n = 1, m =
2, R 1 and * are the same as above. ] The example of synthesis of is shown. That is, the optically active trisoxazoline compound obtained in Scheme 1 is reacted with copper (II) trifluoromethanesulfonate in a nitrogen atmosphere to synthesize an optically active trisoxazoline copper complex.
【００２８】[0028]
【化１６】 Embedded image
【００２９】〔式中、Ｔｆはトリフルオロメタンスルホ
ニル基（ＣＦ3ＳＯ2）を示す。Ｒ2及び＊は前記に同
じ。〕 同様に、式（３）の光学活性トリスオキサゾリン銅錯体
も合成することができる。次に、不斉アリル酸化反応に
ついて説明する。[In the formula, Tf represents a trifluoromethanesulfonyl group (CF 3 SO 2 ). R 2 and * are the same as above. Similarly, the optically active trisoxazoline copper complex of the formula (3) can also be synthesized. Next, the asymmetric allyl oxidation reaction will be described.
【００３０】反応基質である式（５）の環状オレフィン
としては、シクロペンテン、シクロヘキセン、シクロヘ
プテン、シクロオクテン等が挙げられる。酸化剤である
式（６）の過酸エステルとしては、過酢酸、過安息香
酸、過酢酸ｔ−ブチルエステル、過安息香酸ｔ−ブチル
エステル、ｔ−ブチルパーオキシプロパノエート、１，
１−ジメチルプロピルパーオキシピバロエート、ｔ−ブ
チルパーオキシ−２，２−ジメチルプロパノエート等が
挙げられ、好ましくは、過酢酸ｔ−ブチルエステル、過
安息香酸ｔ−ブチルエステル等が挙げられる。Examples of the cyclic olefin of the formula (5) which is a reaction substrate include cyclopentene, cyclohexene, cycloheptene, cyclooctene and the like. As the peracid ester of the formula (6) which is an oxidizing agent, peracetic acid, perbenzoic acid, peracetic acid t-butyl ester, perbenzoic acid t-butyl ester, t-butylperoxypropanoate, 1,
1-Dimethylpropylperoxypivaloate, t-butylperoxy-2,2-dimethylpropanoate and the like can be mentioned, with preference given to peracetic acid t-butyl ester and perbenzoic acid t-butyl ester. .
【００３１】本発明の不斉アリル酸化反応は、光学活性
トリスオキサゾリン化合物と銅化合物及び／又は光学活
性トリスオキサゾリン銅錯体の存在下行うことができ
る。光学活性トリスオキサゾリン化合物と銅化合物を使
用する場合、光学活性トリスオキサゾリン化合物の使用
量は、オレフィンに対して０．１モル％〜５０モル％の
範囲、好ましくは０．１モル％〜１０モル％の範囲であ
る。The asymmetric allyl oxidation reaction of the present invention can be carried out in the presence of an optically active trisoxazoline compound and a copper compound and / or an optically active trisoxazoline copper complex. When the optically active trisoxazoline compound and the copper compound are used, the amount of the optically active trisoxazoline compound used is in the range of 0.1 mol% to 50 mol%, preferably 0.1 mol% to 10 mol% with respect to the olefin. Is the range.
【００３２】銅化合物の使用量は、オレフィンに対して
０．１モル％〜５０モル％の範囲、好ましくは０．１モ
ル％〜１０モル％の範囲である。銅化合物としては、酢
酸第１銅、酢酸第２銅、トリフルオロメタンスルホン酸
第１銅、トリフルオロメタンスルホン酸第２銅、シアン
化第１銅、シアン化第２銅、塩化第１銅、塩化第２銅、
臭化第１銅、臭化第２銅、沃化第１銅、沃化第２銅等が
挙げられ、トリフルオロメタンスルホン酸第１銅、トリ
フルオロメタンスルホン酸第２銅が好ましい。The amount of the copper compound used is in the range of 0.1 mol% to 50 mol%, preferably 0.1 mol% to 10 mol% with respect to the olefin. Examples of the copper compound include cupric acetate, cupric acetate, cupric trifluoromethanesulfonate, cupric trifluoromethanesulfonate, cuprous cyanide, cupric cyanide, cuprous chloride, and cupric chloride. 2 copper,
Examples thereof include cuprous bromide, cupric bromide, cuprous iodide, cupric iodide and the like, and cuprous trifluoromethanesulfonate and cupric trifluoromethanesulfonate are preferable.
【００３３】又、光学活性トリスオキサゾリン銅錯体の
使用量は、オレフィンに対して０．１モル％〜５０モル
％の範囲、好ましくは０．１モル％〜１０モル％の範囲
である。過酸エステルの使用量は、特に制限はないが、
環状オレフィンに対して０．１〜１０倍モル、好ましく
は、０．５〜５倍モルが望ましい。The amount of the optically active trisoxazoline copper complex used is in the range of 0.1 mol% to 50 mol%, preferably 0.1 mol% to 10 mol% with respect to the olefin. The amount of peracid ester used is not particularly limited,
The amount is 0.1 to 10 times mol, preferably 0.5 to 5 times mol, of the cyclic olefin.
【００３４】反応溶媒としては、反応に関与しないもの
であれば特に制限はなく、例えば、アセトニトリル、プ
ロピオニトリル、ブチロニトリル等のニトリル類、アセ
トン、メチルエチルケトン、メチルイソブチルケトン等
のケトン類、ベンゼン、トルエン、キシレン、メシチレ
ン、クロルベンゼン、ｏ−ジクロルベンゼン等の芳香族
炭化水素類、ｎ−ヘキサン、シクロヘキサン、ｎ−オク
タン、ｎ−デカン等の脂肪族炭化水素類、酢酸メチル、
酢酸エチル、酢酸ブチル等のエステル類、ジクロロメタ
ン、ジクロロエタン、四塩化炭素等のハロゲン化炭化水
素類、テトラヒドロフラン、ジエチルエーテル、ｔ−ブ
チルメチルエーテル、ジメトキシエタン等のエーテル
類、メタノール、エタノール、１−プロパノール、２−
プロパノール、１−ブタノール、２−ブタノール、イソ
ブタノール、シクロヘキサノール等のアルコール類等が
挙げられ、好ましくは、アセトン、プロピオニトリル、
ベンゼン、酢酸エチル等が挙げられる。The reaction solvent is not particularly limited as long as it does not participate in the reaction, and examples thereof include nitriles such as acetonitrile, propionitrile and butyronitrile, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, benzene and toluene. , Xylene, mesitylene, chlorobenzene, o-dichlorobenzene and other aromatic hydrocarbons, n-hexane, cyclohexane, n-octane, n-decane and other aliphatic hydrocarbons, methyl acetate,
Esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as dichloromethane, dichloroethane and carbon tetrachloride, ethers such as tetrahydrofuran, diethyl ether, t-butyl methyl ether and dimethoxyethane, methanol, ethanol, 1-propanol , 2-
Examples thereof include alcohols such as propanol, 1-butanol, 2-butanol, isobutanol and cyclohexanol, and preferably acetone, propionitrile,
Examples thereof include benzene and ethyl acetate.
【００３５】又、反応基質である環状オレフィンをその
まま溶媒として使用することもできる。更に、これら溶
媒の使用は、単独又は組み合わせて使用することもでき
る。反応温度は、通常−５０℃〜５０℃、好ましくは−
２５℃〜３０℃の範囲がよい。Further, the reaction substrate cyclic olefin can be used as it is as a solvent. Further, the use of these solvents may be used alone or in combination. The reaction temperature is generally -50 ° C to 50 ° C, preferably-
The range of 25 ° C to 30 ° C is preferable.
【００３６】反応時間は、環状オレフィン及び過酸エス
テルの反応性にもよるが、通常０．１〜１０００時間で
ある。水を加えて反応をクエンチした後適当な溶媒によ
り抽出し、溶媒を減圧濃縮して、シリカゲルカラムクロ
マトグラフィー又は蒸留等により分離すると、目的とす
る光学活性アリルアルコールを単離することができる。The reaction time is usually 0.1 to 1000 hours, although it depends on the reactivity of the cyclic olefin and the perester. The desired optically active allyl alcohol can be isolated by adding water to quench the reaction, extracting with a suitable solvent, concentrating the solvent under reduced pressure, and separating by silica gel column chromatography or distillation.
【００３７】得られた光学活性アリルアルコールの光学
純度は、光学活性クロマトグラフィーカラムや旋光度に
よって分析することができる。The optical purity of the obtained optically active allyl alcohol can be analyzed by an optically active chromatography column or optical rotation.
【００３８】[0038]
【実施例】以下、本発明を実施例を挙げて更に詳しく説
明するが、本発明はこれらに限定されるものではない。 実施例１［光学活性トリスオキサゾリン化合物の合成
（スキーム１において、Ｒ2がフェニル基）］ １．ニトリロ三酢酸トリメチルエステルの合成 ニトリロ三酢酸３０ｇをメタノール２５０ｍｌに溶解し
た溶液に、濃硫酸９ｍｌを加え１０時間加熱、還流し
た。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 [Synthesis of optically active trisoxazoline compound (in Scheme 1, R 2 is a phenyl group)] Synthesis of trimethyl ester of nitrilotriacetic acid To a solution of 30 g of nitrilotriacetic acid dissolved in 250 ml of methanol was added 9 ml of concentrated sulfuric acid, and the mixture was heated and refluxed for 10 hours.
【００３９】室温に戻してから、炭酸カリウム２０ｇを
ゆっくりと加え、無機塩をろ過し、無水硫酸ナトリウム
で乾燥した。濃縮して得られた油状物を減圧蒸留（１７
５℃／２．５ｍｍＨｇ）することにより、ニトリロ三酢
酸トリメチルエステル（無色油状）を６０％の収率で得
た。1 H NMR (CDCl3 270 MHz) : 3.66(9H, s), 3.61(6H, s) IR 1732, 1437, 1271, 1155, 1013 ２．β−ヒドロキシアミドの合成 ニトリロ三酢酸トリメチルエステル１．１１ｇ（４．７
８ｍｍｏｌ）と（Ｓ）−（＋）−フェニルグリシノール
２ｇ（１４．６ｍｍｏｌ）の混合物を８０℃で４０時間
加熱した。After returning to room temperature, 20 g of potassium carbonate was slowly added, inorganic salts were filtered, and dried over anhydrous sodium sulfate. The oily substance obtained by concentration was distilled under reduced pressure (17
5 ° C./2.5 mmHg), nitrilotriacetic acid trimethyl ester (colorless oily substance) was obtained in a yield of 60%. 1 H NMR (CDCl 3 270 MHz): 3.66 (9H, s), 3.61 (6H, s) IR 1732, 1437, 1271, 1155, 1013 2. Synthesis of β-hydroxyamide 1.11 g (4.7% of trimethyl ester of nitrilotriacetic acid
A mixture of 8 mmol) and (S)-(+)-phenylglycinol 2 g (14.6 mmol) was heated at 80 ° C. for 40 hours.
【００４０】得られた粘稠な油状物をシリカゲルカラム
（クロロホルム：メタノール＝１９：１）で精製し、白
色固体のβ−ヒドロキシアミド１．７５ｇ（収率６７
％）を得た。1 H NMR (CDCl3 270MHz) : 8.48(3H, d, J=8.25), 7.16-
7.26(15H, m),5.10(3H, m), 4.58(3H, br s), 3.80-3.7
(6H, m),3.32(3H, d, J=16.5), 3.23(3H, d, J=16.5) IR 3403, 1655, 1556, 1070, 1041, 702 ３．光学活性トリスオキサゾリン化合物の合成 β−ヒドロキシアミド１ｇ（１４．６ｍｍｏｌ）を２０
ｍｌのアセトニトリルに溶かし、トリエチルアミン４ｍ
ｌと四塩化炭素４ｍｌを順次加えた。The viscous oil obtained was purified by a silica gel column (chloroform: methanol = 19: 1) to give 1.75 g of white solid β-hydroxyamide (yield 67.
%) Was obtained. 1 H NMR (CDCl 3 270 MHz): 8.48 (3H, d, J = 8.25), 7.16-
7.26 (15H, m), 5.10 (3H, m), 4.58 (3H, br s), 3.80-3.7
(6H, m), 3.32 (3H, d, J = 16.5), 3.23 (3H, d, J = 16.5) IR 3403, 1655, 1556, 1070, 1041, 702 3. Synthesis of Optically Active Trisoxazoline Compound 20 g of β-hydroxyamide 1 g (14.6 mmol)
Dissolve in ml of acetonitrile, triethylamine 4m
1 and 4 ml of carbon tetrachloride were sequentially added.
【００４１】この溶液に、トリフェニルホスフィン１．
９１ｇ（７．２９ｍｍｏｌ）を室温で一時間かけて加え
た。この混合液を更に一時間撹拌した後、５０ｍｌの飽
和炭酸水素ナトリウム水溶液を加え、酢酸エチルで希釈
した。有機層を飽和塩化ナトリウム水溶液で洗い、無水
硫酸ナトリウム上で乾燥し、ろ過、濃縮した後、シリカ
ゲルカラム（クロロホルム／トリエチルアミン＝１０
０：０−９９：１）で精製し、油状の光学活性トリスオ
キサゾリン化合物３７０ｍｇ（収率４０％）を得た。To this solution was added triphenylphosphine 1.
91 g (7.29 mmol) was added at room temperature over 1 hour. The mixture was stirred for another hour, 50 ml of saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was diluted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, filtered and concentrated, and then a silica gel column (chloroform / triethylamine = 10).
The product was purified with 0: 0-99: 1) to obtain 370 mg (yield 40%) of optically active trisoxazoline compound as an oil.
【００４２】1H NMR (CDCl3 270MHz) : 7.27-7.35(5H,
m), 5.22(1H, dd, J=8.58, 10.22Hz),4.65(1H, dd, J=
8.58, 10.22Hz), 4.11(1H, dd,J=8.58, 8.58Hz), 3.91
(2H,s)13 C NMR (CDCl3 270MHz) : 165.2, 141.9, 128.6, 127.
4, 126.5, 74.52,50.51 IR 1664, 1144, 984, 762, 700 FABMS m/z (rel int) 495.1(135,M H+), 334.1(41.94),
187.1(40.89) 実施例２［光学活性トリスオキサゾリン化合物の合成
（スキーム１において、Ｒ2がイソプロピル基）］ １．β−ヒドロキシアミドの合成 実施例１の（Ｓ）−（＋）−フェニルグリシノールの代
わりに、（Ｓ）−（＋）−バリノールを使用する以外は
実施例１と同様に反応させて、白色固体のβ−ヒドロキ
シアミドを得た（収率９４％）。 1 H NMR (CDCl 3 270 MHz): 7.27-7.35 (5H,
m), 5.22 (1H, dd, J = 8.58, 10.22Hz), 4.65 (1H, dd, J =
8.58, 10.22Hz), 4.11 (1H, dd, J = 8.58, 8.58Hz), 3.91
(2H, s) 13 C NMR (CDCl 3 270MHz): 165.2, 141.9, 128.6, 127.
4, 126.5, 74.52, 50.51 IR 1664, 1144, 984, 762, 700 FABMS m / z (rel int) 495.1 (135, M H +), 334.1 (41.94),
187.1 (40.89) Example 2 [Synthesis of optically active trisoxazoline compound (in Scheme 1, R 2 is an isopropyl group)] Synthesis of β-hydroxyamide White reaction was performed in the same manner as in Example 1 except that (S)-(+)-valinol was used instead of (S)-(+)-phenylglycinol in Example 1. Solid β-hydroxyamide was obtained (yield 94%).
【００４３】1H NMR (CDCl3 270MHz) : 7.44(3H, d, J=
8.9), 4.30(3H, br s), 3.79-3.51(9H, m), 3.46(3H,
m), 3.36(3H, d, J=16), 1.81(3H, m), 0.93(9H, d, J=
16.5), 0.90(9H, d,J=6.9) IR 3433, 2964, 2877, 1650, 1550 ２．光学活性トリスオキサゾリン化合物の合成 上記β−ヒドロキシアミドを使用する以外は実施例１と
同様に反応させて、油状の光学活性トリスオキサゾリン
化合物を得た（収率２４％）。 1 H NMR (CDCl 3 270 MHz): 7.44 (3 H, d, J =
8.9), 4.30 (3H, br s), 3.79-3.51 (9H, m), 3.46 (3H,
m), 3.36 (3H, d, J = 16), 1.81 (3H, m), 0.93 (9H, d, J =
16.5), 0.90 (9H, d, J = 6.9) IR 3433, 2964, 2877, 1650, 1550 2. Synthesis of Optically Active Trisoxazoline Compound An oily optically active trisoxazoline compound was obtained by the same reaction as in Example 1 except that the above β-hydroxyamide was used (yield 24%).
【００４４】1H NMR (CDCl3 270MHz) : 4.25(1H, m),
3.78-4.01(2H, m), 3.64(2H, s),1.73(1H, m), 0.96(1
H, d, J=6.6Hz), 0.88(1H, d,J=6.6Hz) IR 2960, 2931, 2906, 2873, 1670 FABMS m/z (rel int) 393.5(148. 46,M H+), 266.4(60.
43) 実施例３［光学活性トリスオキサゾリン銅錯体の合成
（スキーム２において、Ｒ2がフェニル基）］ 窒素雰囲気下、トリフルオロメタンスルホン酸銅（II）
２９０ｍｇに、実施例１の光学活性オキサゾリン化合物
４６０ｍｇを無水アセトニトリル３ｍｌの溶液として加
え、室温で２時間撹拌した。 1 H NMR (CDCl 3 270 MHz): 4.25 (1 H, m),
3.78-4.01 (2H, m), 3.64 (2H, s), 1.73 (1H, m), 0.96 (1
H, d, J = 6.6Hz), 0.88 (1H, d, J = 6.6Hz) IR 2960, 2931, 2906, 2873, 1670 FABMS m / z (rel int) 393.5 (148.46, M H +), 266.4 (60.
43) Example 3 [Synthesis of optically active trisoxazoline copper complex (R 2 is a phenyl group in Scheme 2)] Copper (II) trifluoromethanesulfonate under a nitrogen atmosphere
To 290 mg, 460 mg of the optically active oxazoline compound of Example 1 was added as a solution in 3 ml of anhydrous acetonitrile, and the mixture was stirred at room temperature for 2 hours.
【００４５】この溶液に無水ジエチルエーテル２４ｍｌ
を加え上澄みを取り除き、更に生成した不溶の緑色油状
物を５ｍｌの無水ジエチルエーテルで洗った。この油状
物を減圧下（２ｍｍＨｇ）５０℃で乾燥し、光学活性ト
リスオキサゾリン銅錯体５００ｍｇを緑色の粉末として
得た（収率７３％）。 IR 3458, 2359, 1649, 1271, 1171, 1034 FABMS m/z (rel int) 706.3(14.37, １-CuOTf+), 557.4
(32.78, １-Cu+) 実施例４ 窒素雰囲気下、トリフルオロメタンスルホン酸銅（II）
４ｍｇ（１１μｍｏｌ）に、実施例１の光学活性トリス
オキサゾリン化合物８．２ｍｇ（１７μｍｏｌ）のアセ
トン溶液（９０μｌ）を加え、室温で１時間撹拌した。24 ml of anhydrous diethyl ether was added to this solution.
Was added to remove the supernatant, and the resulting insoluble green oily substance was washed with 5 ml of anhydrous diethyl ether. This oily substance was dried under reduced pressure (2 mmHg) at 50 ° C. to obtain 500 mg of an optically active trisoxazoline copper complex as a green powder (yield 73%). IR 3458, 2359, 1649, 1271, 1171, 1034 FABMS m / z (rel int) 706.3 (14.37, 1-CuOTf +), 557.4
(32.78, 1-Cu +) Example 4 Copper (II) trifluoromethanesulfonate under nitrogen atmosphere
An acetone solution (90 μl) of 8.2 mg (17 μmol) of the optically active trisoxazoline compound of Example 1 was added to 4 mg (11 μmol), and the mixture was stirred at room temperature for 1 hour.
【００４６】この溶液にアセトン０．３４ｍｌとシクロ
ペンテン６０ｍｇ（０．８８ｍｍｏｌ）を加えて、０℃
に冷却した。次に、過安息香酸ｔ−ブチルエステル４２
μｇ（０．２２ｍｍｏｌ）を徐々に加えて、０℃で９２
時間撹拌した。反応終了後、水０．５ｍｌを加えて、混
合物をエーテルで抽出した。To this solution, 0.34 ml of acetone and 60 mg (0.88 mmol) of cyclopentene were added, and the mixture was added at 0 ° C.
And cooled. Next, perbenzoic acid t-butyl ester 42
μg (0.22 mmol) was added slowly and the mixture was added at 0 ° C. to 92
Stirred for hours. After the reaction was completed, 0.5 ml of water was added and the mixture was extracted with ether.
【００４７】エーテル層を２ＮＨＣｌ及び水で洗って、
無水硫酸ナトリウムで乾燥し、濃縮した。残渣をシリカ
ゲルカラムクロマトグラフィー（溶出溶媒：ヘキサン／
酢酸エチル＝９９：１）により精製し、白色油状の
（Ｓ）−２−シクロペンテニルベンゾエート１８．２ｍ
ｇ（収率４４％）を得た。不斉収率：８４％ｅｅ。絶対
配位：Ｓ（Ｄａｉｃｅｌ Ｃｈｉｒａｌｃｅｌ ＯＤ，
ヘキサン／イソプロパノール＝１０００／１） 実施例５〜１０ 溶媒及び反応温度を変更した他は実施例４と同様に不斉
アリル酸化反応を行なった結果を下表に示す。The ether layer was washed with 2N HCl and water,
Dried over anhydrous sodium sulfate and concentrated. The residue was subjected to silica gel column chromatography (elution solvent: hexane /
Purified by ethyl acetate = 99: 1), white oily (S) -2-cyclopentenyl benzoate 18.2 m
g (44% yield). Asymmetric yield: 84% ee. Absolute coordination: S (Daicel Chiralcel OD,
Hexane / isopropanol = 1000/1) Examples 5 to 10 The following table shows the results of the asymmetric allylic oxidation reaction as in Example 4 except that the solvent and the reaction temperature were changed.
【００４８】[0048]
【表１】 実施例１１〜１４ シクロペンテンの代わりにシクロヘキセンを使用し、実
施例４と同様に不斉アリル酸化反応を行なった結果を下
表に示す。[Table 1] Examples 11 to 14 The following table shows the results of carrying out an asymmetric allylic oxidation reaction in the same manner as in Example 4 using cyclohexene instead of cyclopentene.
【００４９】但し、光学純度は、Ｄａｉｃｅｌ Ｃｈｉ
ｒａｌｃｅｌ ＡＤ，ヘキサン／イソプロパノール＝１
０００／１で決定した。However, the optical purity is based on Daicel Chi.
ralcel AD, hexane / isopropanol = 1
It was determined at 000/1.
【００５０】[0050]
【表２】 実施例１５ シクロペンテンの代わりにシクロヘプテンを使用し、実
施例４と同様に不斉アリル酸化反応を行なった結果を下
表に示す。[Table 2] Example 15 The following table shows the results of carrying out an asymmetric allylic oxidation reaction in the same manner as in Example 4 except that cycloheptene was used instead of cyclopentene.
【００５１】但し、光学純度は、1ＨＮＭＲ（２７０Ｍ
Ｈｚ，キラルシフト剤：［Ｅｕ（ｈｆｃ）３］）で決定
した。However, the optical purity is 1 HNMR (270M
Hz, chiral shift agent: [Eu (hfc) 3]).
【００５２】[0052]
【表３】 実施例１６ シクロペンテンの代わりにシクロオクテンを使用し、実
施例４と同様に不斉アリル酸化反応を行なった結果を下
表に示す。[Table 3] Example 16 The following table shows the result of carrying out an asymmetric allylic oxidation reaction in the same manner as in Example 4 except that cyclooctene was used instead of cyclopentene.
【００５３】但し、光学純度は、1ＨＮＭＲ（２７０Ｍ
Ｈｚ，キラルシフト剤：［Ｅｕ（ｈｆｃ）３］）で決定
した。However, the optical purity is 1 HNMR (270M
Hz, chiral shift agent: [Eu (hfc) 3]).
【００５４】[0054]
【表４】 [Table 4]
【００５５】[0055]
【発明の効果】本発明の式（１）及び式（２）の光学活
性トリスオキサゾリン化合物は、金属に対する配位子と
して有効であり、特に不斉アリル酸化反応に於ける銅触
媒の配位子として使用することにより、式（５）のオレ
フィンから、医農薬及びその中間体として有用な式
（７）の光学活性アリルアルコールを容易に製造するこ
とができる。INDUSTRIAL APPLICABILITY The optically active trisoxazoline compounds of the formulas (1) and (2) of the present invention are effective as a ligand for a metal, and particularly, a ligand of a copper catalyst in an asymmetric allylic oxidation reaction. When used as, the optically active allyl alcohol of the formula (7), which is useful as a pharmaceutical and agricultural chemical and its intermediate, can be easily produced from the olefin of the formula (5).
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 69/76 Ｃ０７Ｃ 69/76 Ｚ Ｃ０７Ｄ 263/12 Ｃ０７Ｄ 263/12 263/14 263/14 Ｃ０７Ｆ 1/08 Ｃ０７Ｆ 1/08 Ｃ // Ｃ０７Ｍ 7:00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07C 69/76 C07C 69/76 Z C07D 263/12 C07D 263/12 263/14 263/14 C07F 1 / 08 C07F 1/08 C // C07M 7:00
Claims (16)
ル基、フェニル基（該フェニル基は、ハロゲン原子、Ｃ
1〜6アルキル基、Ｃ1〜6アルコキシ基で置換されていて
もよい。）、ベンジル基（該ベンジル基は、ハロゲン原
子、Ｃ1〜6アルキル基、Ｃ1〜6アルコキシ基で置換され
ていてもよい。）を示す。ｎは１〜３の整数を示す。＊
は不斉炭素原子を示し、その炭素原子の絶対配置はＲか
Ｓを意味する。〕で表わされる光学活性トリスオキサゾ
リン化合物。(1) Formula (1) Or formula (2) Wherein, R 1 and R 2 are each independently, C 1 ~ 6 alkyl group, a phenyl group (the phenyl group, a halogen atom, C
1-6 alkyl group, optionally substituted with C 1-6 alkoxy groups. ), Benzyl group (said benzyl group, a halogen atom, C 1 ~ 6 alkyl group, optionally substituted with C 1 ~ 6 alkoxy group.). n shows the integer of 1-3. *
Represents an asymmetric carbon atom, and the absolute configuration of the carbon atom means R or S. ] The optically active trisoxazoline compound represented by these.
リスオキサゾリン化合物。2. The optically active trisoxazoline compound according to claim 1, wherein n is 1.
光学活性トリスオキサゾリン化合物。3. The optically active trisoxazoline compound according to claim 2, wherein R 2 is a phenyl group.
載の光学活性トリスオキサゾリン化合物。4. The optically active trisoxazoline compound according to claim 2, wherein R 2 is an isopropyl group.
ル基、フェニル基（該フェニル基は、ハロゲン原子、Ｃ
1〜6アルキル基、Ｃ1〜6アルコキシ基で置換されていて
もよい。）、ベンジル基（該ベンジル基は、ハロゲン原
子、Ｃ1〜6アルキル基、Ｃ1〜6アルコキシ基で置換され
ていてもよい。）を示す。Ｘは、アセトキシ基、トリフ
ルオロメタンスルホニル基、シアノ基、ハロゲン原子を
示す。ｎは１〜３の整数を示し、ｍは１又は２の整数を
示す。＊は不斉炭素原子を示し、その炭素原子の絶対配
置はＲかＳを意味する。〕で表わされる光学活性トリス
オキサゾリン銅錯体。5. A formula (3): Or formula (4) Wherein, R 1 and R 2 are each independently, C 1 ~ 6 alkyl group, a phenyl group (the phenyl group, a halogen atom, C
1-6 alkyl group, optionally substituted with C 1-6 alkoxy groups. ), Benzyl group (said benzyl group, a halogen atom, C 1 ~ 6 alkyl group, optionally substituted with C 1 ~ 6 alkoxy group.). X represents an acetoxy group, a trifluoromethanesulfonyl group, a cyano group, or a halogen atom. n represents an integer of 1 to 3 and m represents an integer of 1 or 2. * Indicates an asymmetric carbon atom, and the absolute configuration of the carbon atom means R or S. ] The optically active trisoxazoline copper complex represented by these.
リスオキサゾリン銅錯体。6. The optically active trisoxazoline copper complex according to claim 5, wherein n is 1.
光学活性トリスオキサゾリン銅錯体。7. The optically active trisoxazoline copper complex according to claim 6, wherein R 2 is a phenyl group.
載の光学活性トリスオキサゾリン銅錯体。8. The optically active trisoxazoline copper complex according to claim 6, wherein R 2 is an isopropyl group.
ｍが２である請求項７又は請求項８記載の光学活性トリ
スオキサゾリン銅錯体。9. X is a trifluoromethanesulfonyl group,
The optically active trisoxazoline copper complex according to claim 7 or 8, wherein m is 2.
環状オレフィンと、式（６） 【化６】 〔式中、Ｗは、Ｃ1〜8アルキル基、フェニル基（該フェ
ニル基は、ハロゲン原子、Ｃ1〜6アルキル基、Ｃ1〜6ア
ルコキシ基で置換されていてもよい。）を示す。Ｚは、
水素原子又はＣ1〜8アルキル基を示す。〕で表わされる
過酸エステルを、請求項１記載の光学活性トリスオキサ
ゾリン化合物を配位子とする銅錯体及び／又は請求項５
記載の光学活性トリスオキサゾリン銅錯体の存在下、反
応させて、式（７） 【化７】 〔式中、＊は不斉炭素原子を示し、その炭素原子の絶対
配置はＲかＳを意味する。〕Ｗ及びｒは前記に同じ。〕
で表わされる光学活性アリルアルコールを得ることを特
徴とするオレフィンの不斉アリル酸化反応。10. Formula (5): [In formula, r means the integer of 1-4. ] And a cyclic olefin represented by the formula (6): Wherein, W is, C 1 ~ 8 alkyl group, a phenyl group (the phenyl group, a halogen atom, C 1 ~ 6 alkyl group, optionally substituted with C 1 ~ 6 alkoxy group.) Shows a. Z is
It represents a hydrogen atom or a C 1 ~ 8 alkyl group. ] The perester represented by the formula [7] and a copper complex having the optically active trisoxazoline compound according to claim 1 as a ligand and / or 5
By reacting in the presence of the optically active trisoxazoline copper complex described in the formula (7): [In the formula, * represents an asymmetric carbon atom, and the absolute configuration of the carbon atom means R or S. ] W and r are the same as the above. ]
Asymmetric allylic oxidation of olefins characterized by obtaining optically active allyl alcohol represented by
リンを配位子とする銅錯体及び／又は光学活性トリスオ
キサゾリン銅錯体を使用することを特徴とする請求項１
０記載の不斉アリル酸化反応。11. A copper complex having an optically active trisoxazoline as a ligand, in which n is 1, and / or an optically active trisoxazoline copper complex is used.
Asymmetric allylic oxidation reaction described in 0.
スオキサゾリンを配位子とする銅錯体及び／又は光学活
性トリスオキサゾリン銅錯体を使用することを特徴とす
る請求項１０記載の不斉アリル酸化反応。12. The asymmetric allylic oxidation according to claim 10, wherein a copper complex having an optically active trisoxazoline as a ligand and / or an optically active trisoxazoline copper complex in which R 2 is a phenyl group is used. reaction.
トリスオキサゾリンを配位子とする銅錯体及び／又は光
学活性トリスオキサゾリン銅錯体を使用することを特徴
とする請求項１０記載の不斉アリル酸化反応。13. The asymmetric allylic oxidation according to claim 10, wherein a copper complex having an optically active trisoxazoline as a ligand and / or an optically active trisoxazoline copper complex in which R 2 is an isopropyl group is used. reaction.
基、ｍが２である光学活性トリスオキサゾリン銅錯体を
使用することを特徴とする請求項１２又は請求項１３記
載の不斉アリル酸化反応。14. The asymmetric allylic oxidation reaction according to claim 12, wherein an optically active trisoxazoline copper complex in which X is a trifluoromethanesulfonyl group and m is 2 is used.
ることを特徴とする請求項１０記載の不斉アリル酸化反
応。15. The asymmetric allylic oxidation reaction according to claim 10, wherein the cyclic olefin is cyclopentene.
エステルであることを特徴とする請求項１０記載の不斉
アリル酸化反応。16. The asymmetric allylic oxidation reaction according to claim 10, wherein the peracid ester is perbenzoic acid t-butyl ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1868296A JPH09208566A (en) | 1996-02-05 | 1996-02-05 | Optically active oxazoline compound and asymmetric allyl oxidization reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1868296A JPH09208566A (en) | 1996-02-05 | 1996-02-05 | Optically active oxazoline compound and asymmetric allyl oxidization reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09208566A true JPH09208566A (en) | 1997-08-12 |
Family
ID=11978388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1868296A Pending JPH09208566A (en) | 1996-02-05 | 1996-02-05 | Optically active oxazoline compound and asymmetric allyl oxidization reaction |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09208566A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001294580A (en) * | 2000-04-14 | 2001-10-23 | Nissan Chem Ind Ltd | Optically active oxazoline compound and method for producing optically active allyl alcohol derivative by using the compound |
-
1996
- 1996-02-05 JP JP1868296A patent/JPH09208566A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001294580A (en) * | 2000-04-14 | 2001-10-23 | Nissan Chem Ind Ltd | Optically active oxazoline compound and method for producing optically active allyl alcohol derivative by using the compound |
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