JP7164647B2 - 金属錯体 - Google Patents
金属錯体 Download PDFInfo
- Publication number
- JP7164647B2 JP7164647B2 JP2021035264A JP2021035264A JP7164647B2 JP 7164647 B2 JP7164647 B2 JP 7164647B2 JP 2021035264 A JP2021035264 A JP 2021035264A JP 2021035264 A JP2021035264 A JP 2021035264A JP 7164647 B2 JP7164647 B2 JP 7164647B2
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- JP
- Japan
- Prior art keywords
- ion
- mmol
- metal complex
- trans
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000004696 coordination complex Chemical class 0.000 title claims description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 120
- -1 fluorite ion Chemical class 0.000 claims description 86
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 229910052741 iridium Inorganic materials 0.000 claims description 30
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 30
- 150000001412 amines Chemical class 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 125000004429 atom Chemical group 0.000 claims description 17
- 125000005843 halogen group Chemical group 0.000 claims description 17
- 239000011541 reaction mixture Substances 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 9
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 8
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 125000004008 6 membered carbocyclic group Chemical group 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 5
- 150000003003 phosphines Chemical class 0.000 claims description 5
- 125000006570 (C5-C6) heteroaryl group Chemical group 0.000 claims description 4
- 125000001054 5 membered carbocyclic group Chemical group 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000005330 8 membered heterocyclic group Chemical group 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical group [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 3
- DKSMCEUSSQTGBK-UHFFFAOYSA-M bromite Chemical compound [O-]Br=O DKSMCEUSSQTGBK-UHFFFAOYSA-M 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- LLYCMZGLHLKPPU-UHFFFAOYSA-M perbromate Chemical compound [O-]Br(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-M 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 2
- 229940005989 chlorate ion Drugs 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-M chlorite Chemical compound [O-]Cl=O QBWCMBCROVPCKQ-UHFFFAOYSA-M 0.000 claims description 2
- 229940005993 chlorite ion Drugs 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 2
- BLBIZNCSZLTDPW-UHFFFAOYSA-N dihydrogenphosphite Chemical compound OP(O)[O-] BLBIZNCSZLTDPW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010436 fluorite Substances 0.000 claims description 2
- 229940079826 hydrogen sulfite Drugs 0.000 claims description 2
- GBHRVZIGDIUCJB-UHFFFAOYSA-N hydrogenphosphite Chemical compound OP([O-])[O-] GBHRVZIGDIUCJB-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 229940005654 nitrite ion Drugs 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-M oxalate(1-) Chemical compound OC(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229940006280 thiosulfate ion Drugs 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 2
- 125000006569 (C5-C6) heterocyclic group Chemical group 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 claims 1
- 229940063013 borate ion Drugs 0.000 claims 1
- 229940006460 bromide ion Drugs 0.000 claims 1
- 150000002222 fluorine compounds Chemical group 0.000 claims 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims 1
- 229940005633 iodate ion Drugs 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical group [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims 1
- 229940006461 iodide ion Drugs 0.000 claims 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-M periodate Chemical compound [O-]I(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-M 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 80
- 238000005481 NMR spectroscopy Methods 0.000 description 62
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 57
- 239000000460 chlorine Substances 0.000 description 51
- 239000000203 mixture Substances 0.000 description 50
- 238000006243 chemical reaction Methods 0.000 description 49
- 239000010948 rhodium Substances 0.000 description 49
- 239000000543 intermediate Substances 0.000 description 44
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 43
- 238000000746 purification Methods 0.000 description 39
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 25
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 24
- 239000000725 suspension Substances 0.000 description 24
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 22
- 238000003818 flash chromatography Methods 0.000 description 22
- 150000002503 iridium Chemical class 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 22
- 125000001424 substituent group Chemical group 0.000 description 22
- 229910052703 rhodium Inorganic materials 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- 229910004298 SiO 2 Inorganic materials 0.000 description 20
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 238000010992 reflux Methods 0.000 description 19
- UILZQFGKPHAAOU-ARJAWSKDSA-N (z)-2-bromobut-2-ene Chemical compound C\C=C(\C)Br UILZQFGKPHAAOU-ARJAWSKDSA-N 0.000 description 18
- 238000000921 elemental analysis Methods 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 15
- 239000013078 crystal Substances 0.000 description 15
- 125000005842 heteroatom Chemical group 0.000 description 15
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 229920006395 saturated elastomer Polymers 0.000 description 15
- 239000007832 Na2SO4 Substances 0.000 description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 description 14
- 235000011152 sodium sulphate Nutrition 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 230000007935 neutral effect Effects 0.000 description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 11
- 238000001953 recrystallisation Methods 0.000 description 11
- 239000011734 sodium Chemical class 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 239000012230 colorless oil Substances 0.000 description 8
- 125000002524 organometallic group Chemical group 0.000 description 8
- 150000003283 rhodium Chemical class 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000001979 organolithium group Chemical group 0.000 description 6
- 150000004684 trihydrates Chemical class 0.000 description 6
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 5
- VURFVHCLMJOLKN-UHFFFAOYSA-N Diphosphine Natural products PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000007126 N-alkylation reaction Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000004982 aromatic amines Chemical class 0.000 description 5
- 235000013877 carbamide Nutrition 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 125000002950 monocyclic group Chemical group 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 125000006239 protecting group Chemical group 0.000 description 5
- 150000003333 secondary alcohols Chemical class 0.000 description 5
- 239000012453 solvate Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000002837 carbocyclic group Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 4
- 239000002815 homogeneous catalyst Substances 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003138 primary alcohols Chemical class 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
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- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Chemical class 0.000 description 1
- 239000011701 zinc Chemical class 0.000 description 1
Images
Classifications
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- 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
- C07F17/00—Metallocenes
-
- 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
- B01J31/1805—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 nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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Description
Mは、遷移金属であり、
L1及びL2は、独立に、ハロゲン、ニトリル、アミン、ホスフィン、ホスファイト、スルホン酸エステル、N-複素環式カルベン、又は5員若しくは6員の複素環から選択され、又はL1及びL2は、一緒になって、ジアミン、ジホスフィン、ジホスファイト、ジスルホン酸エステル、アミノ酸又はその誘導体、アミノアルコール、アミノスルホンアミド、N-複素環式カルベン、ジケトネート、及び置換又は非置換ビピリジンから選択される二座配位子であり、
ここで、L1基及びL2基は、非置換であり、又はハロ、C1~4アルキル、C1~4ハロアルキル、-ORA、-NRARB、-CN、-SO2RAで任意選択で置換されており、
R1及びR2は、それぞれ独立に、H、置換された又は非置換の、C1~14アルキル、C1~14ハロアルキル、C3~8炭素環、及び3~8員の複素環、フェニル置換C1~14アルキル、フルオラスタグ又は固体支持体を表し、
又はR1及びR2は、一緒になって3~8員の複素環を形成し、
R3及びR4は、それぞれ独立に、H、ハロ、C1~6アルキル、C1~6ハロアルキル、C3~6シクロアルキル、及び-ORA1から選択され、
又はR3及びR4は、それらが結合している、共有の、隣接の又は非隣接の炭素原子と共に3~8員の炭素環(任意選択で5員又は6員の炭素環)を一緒に形成し、
又はR1及びR2のうちの1つと、R3及びR4のうちの1つとは、それらが結合している原子と一緒になって3~8員の複素環を形成し、
R5は、ハロ、C1~6アルキル、C1~6ハロアルキル及びC3~6シクロアルキル、C6アリール、又は5員若しくは6員のヘテロアリールから選択され、
又は2つの隣接するR5基は、それらが結合している原子と一緒になって5員若しくは6員の炭素環を形成し、
pは、0又は1以上であり、
nは、1~10から選択され、
mは、0、1、2、3又は4から選択され、
RA、RB及びRA1は、各出現において、独立に、H、C1~6アルキル又はC1~6ハロアルキルから選択される)
の金属錯体が提供される。
による化合物を提供する。
ここで、L1基及びL2基は、非置換であり、又はハロ、C1~4アルキル、C1~4ハロアルキル、-ORA、-NRARB、-CN、-SO2RAで任意選択で置換されている。
ここで、L1基及びL2基は、非置換であり、又はハロ、C1~4アルキル、C1~4ハロアルキル、-ORA、-NRARB、-CN、-SO2RAで任意選択で置換されている。
ここで、L1基及びL2基は、非置換であり、又はハロ、C1~4アルキル、C1~4ハロアルキル、-ORA、-NRARB、-CN、-SO2RAで任意選択で置換されている。
ここで、L1基及びL2基は、非置換であり、又はハロ、C1~4アルキル、C1~4ハロアルキル、-ORA、-NRARB、-CN、-SO2RAで任意選択で置換されている。
(i)本発明の化合物を、所望の酸又は塩基と反応させることによって
(ii)本発明の化合物の好適な前駆体から、酸不安定性保護基若しくは塩基不安定性保護基を除去することによって、又は所望の酸若しくは塩基を使用して、好適な環状前駆体、例えばラクトン若しくはラクタムを開環することによって
(iii)本発明の化合物のうちの1種の塩を、適当な酸若しくは塩基と反応させることにより又は好適なイオン交換カラムの手段により、別の塩に変換することによって。
又は(iv)塩メタセシスによって。
中間体1:N-Boc-4-(2’-アミノエチル)-3,5-ジメチル-ヘプタ-2,5-ジエン-4-オール
Rf=0.30(ヘキサン-EtOAc 80:20);1H NMR(500MHz,CDCl3,δ/ppm):5.65-5.59(2H,m,トランス-トランス異性体の2CH),5.44-5.34(2H,m,トランス-シス異性体の2CH),5.18-5.10(2H,m,2NH),3.30-3.22(4H,m,2H-2’),1.95-1.86(4H,m,2H-1’),1.77(6H,s,2CH3),1.69-1.60(18H,m,6CH3),1.44(18H,s,2C(CH3)3);13C NMR(125MHz,CDCl3,δ/ppm):156.1(C(O)),139.7(CqCH3),139.0(CqCH3),137.7(CqCH3),123.1(トランス-シス異性体のCH),118.6(トランス-トランス異性体のCH),80.7(C(CH3)3),79.8(C-4),78.9(C-4),39.1(C-1’),36.7(C-2’),28.4(C(CH3)3),23.3(CH3),22.7(CH3),14.7(CH3),14.4(CH3),13.2(CH3),12.5(CH3);IR(νmax,ニート,cm-1):3387(N-HとO-H),2976,2933,1696(C=O),1509,1452,1366,1279,1250,1173;HRMS(ESI+)m/z:C16H29NNaO3(M+Na+)の計算値:306.2040,実測値:306.2034。
Rf=0.60(ヘキサン-EtOAc 70:30);1H NMR(500MHz,CDCl3,δ/ppm):5.58(2H,dq,J=1.0,6.5Hz,トランス-トランス異性体の2CH),5.35(2H,dq,J=1.0,6.5Hz,トランス-シス異性体の2CH),4.59(2H,br s,2NH),3.14(4H,br s,2H-3’),1.84-1.81(2H,m,2OH),1.76-1.75(4H,m,2H-1’),1.67-1.59(24H,m,8CH3),1.53-1.49(4H,m,2H-2’),1.43(18H,s,2C(CH3)3);13C NMR(125MHz,CDCl3,δ/ppm):156.1(C(O)),140.0(CqCH3),139.5(CqCH3),138.0(CqCH3),122.7(トランス-シス異性体のCH),122.6(トランス-シス異性体のCH),118.3(トランス-トランス異性体のCH),80.6(C(CH3)3),79.5(C-4),79.0(C-4),41.1(C-3’),36.8(C-1’),35.0(C-1’),28.4(C(CH3)3),24.5(C-2’),24.2(C-2’),23.4(CH3),22.8(CH3),14.7(CH3),14.4(CH3),13.2(CH3),12.6(CH3);HRMS(ESI+)m/z:C17H31NNaO3(M+Na+)の計算値:320.2196,実測値:320.2200.分光学的データは文献値(M.Ito,N.Tejima,M.Yamamura,Y.Endo及びT.Ikariya,Organometallics,2010,29,1886~1889)と一致している。
Rf=0.50(ヘキサン-EtOAc 70:30);1H NMR(500MHz,CDCl3,δ/ppm):5.57(2H,q,J=6.5Hz,トランス-トランス異性体の2CH),5.34(2H,dq,J=1.3,7.5Hz,トランス-シス異性体の2CH),4.54(2H,br s,2NH),3.12(4H,br s,2H-4’),1.84-1.71(6H,m,2H-1’と2OH),1.69-1.60(24H,m,8CH3),1.53-1.46(8H,m,4CH2),1.44(18H,s,2C(CH3)3);13C NMR(125MHz,CDCl3,δ/ppm):156.1(C(O)N),140.2(CqCH3),139.6(CqCH3),138.1(CqCH3),122.5(トランス-シス異性体のCH),122.4(トランス-シス異性体のCH),118.9(トランス-トランス異性体のCH),118.1(トランス-トランス異性体のCH),80.8(C(CH3)3),79.4(C-4),79.1(C-4),40.4(C-4’),39.4(C-1’),37.6(C-1’),28.4(C(CH3)3),23.4(CH3),22.8(CH3),20.7(CH2),20.5(CH2),14.8(CH3),14.4(CH3),13.4(CH3),13.2(CH3),12.6(CH3),12.4(CH3);IR(νmax,ニート,cm-1):3364(N-HとO-H),2975,2933,2865,1695(C=O),1515,1454,1366,1251,1172,1003;HRMS(ESI+)m/z:C18H33NNaO3(M+Na+)の計算値:334.2353,実測値:334.2357。
Rf=0.40(ヘキサン-EtOAc 80:20);1H NMR(500MHz,CDCl3,δ/ppm):5.62-5.56(2H,m,トランス-トランス異性体の2CH),5.42-5.30(2H,m,トランス-シス異性体の2CH),3.27-3.24(4H,m,2H-3’),2.87(6H,br s,2H-1’’),1.86-1.76(4H,m,2H-1’),1.74(2H,s,2OH),1.69-1.61(18H,m,6CH3),1.62-1.59(4H,m,2CH2),1.46(24H,s,2CH3と2C(CH3)3);13C NMR(125MHz,CDCl3,δ/ppm):156.0(C(O)N),140.1(CqCH3),139.6(CqCH3),138.1(CqCH3),122.5(CH),119.0(CH),118.2(CH),80.7(C(CH3)3),79.1(C-4),51.6(C-3’),34.0(C-1’’),29.7(C-1’),28.4(C(CH3)3),23.4(CH3),22.8(CH3),21.9(C-2’),14.8(CH3),14.4(CH3),13.4(CH3),13.2(CH3),12.6(CH3),12.4(CH3);IR(νmax,ニート,cm-1):3474(O-H),2973,2931,1759(C=O),1695(C=C),1481,1454,1395,1365,1171;HRMS(ESI+)m/z:C18H33NNaO3(M+Na+)の計算値:334.2353,実測値:334.2349。
Rf=0.38(DCM-MeOH 80:20);1H NMR(500MHz,CDCl3,δ/ppm):5.65(2H,q,J=5.7Hz,トランス-トランス異性体の2CH),5.58(1H,q,J=6.5Hz,トランス-シス異性体のCH),5.40(1H,q,J=7.3Hz,トランス-シス異性体のCH),2.33-2.28(4H,m,2CH2),2.24(6H,s,2H-1’’),2.20(6H,s,2H-1’’),2.07-1.91(4H,m,2CH2),1.83-1.61(18H,m,6CH3),1.59-1.51(4H,m,2CH2),1.49-1.46(6H,m,2CH3);13C NMR(125MHz,CDCl3,δ/ppm):139.8(CqCH3),139.0(CqCH3),138.8(CqCH3),122.9(トランス-シス異性体のCH),118.5(トランス-トランス異性体のCH),117.5(トランス-シス異性体のCH),79.8(C-4),78.9(C-4),60.6(C-3’),45.1(C-1’’),37.6(C-1’),36.4(C-1’),23.6(CH3),22.1(CH2),21.9(CH2),14.8(CH3),13.5(CH3),13.3(CH3),12.5(CH3),12.4(CH3);IR(νmax,ニート,cm-1):3394(O-H),2944,2919,2859,2821,2779,1459,1378,1039,1014;HRMS(ESI+)m/z:C14H28NO(M+H+)の計算値:226.2165,実測値:226.2167。
Rf=0.50(DCM-MeOH 90:10);mp 117.5-118.6℃(DCM-Et2O);1H NMR(500MHz,CDCl3,δ/ppm):8.54(1H,br s,NH),2.73-2.66(2H,m,H-1),2.68-2.41(1H,m,CH),2.59-2.53(6H,m,2H-1’),2.48-2.23(2H,m,CH2),1.92-1.63(2H,m,CH2),1.80-1.75(9H,m,3CH3),0.98(3H,d,J=7.5Hz,CH3);13C NMR(125MHz,CDCl3,δ/ppm):139.7(CqCH3),139.6(CqCH3),139.0(CqCH3),136.7(CqCH3),136.4(CqCH3),136.1(CqCH3),134.5(CqCH3),133.9(CqCH3),132.9(CqCH3),58.6(C-1),58.2(C-1),55.3(CH),51.6(CH),49.1(CH),43.7(C-1’),43.6(C-1’),43.5(CH2),43.3(CH2),25.8(CH2),25.1(CH2),24.7(CH2),23.3(CH2),22.9(CH2),14.2(CH3),11.9(CH3),11.8(CH3),11.6(CH3),11.3(CH3),11.0(CH3);IR(νmax,ニート,cm-1):3403(N-H),2961,2856,2763,2580,2517,2479,1655,1487,1443,1377,1172,1058,1041,1020,1006;HRMS(ESI+)m/z:C14H26N(M+H+)の計算値:208.2060,実測値:208.2062。
1H NMR(500MHz,CDCl3,δ/ppm):6.67(1H,br s,NH),4.13(2H,q,J=7.0Hz,OCH2),3.98(2H,s,H-2’),3.83(2H,t,J=6.4Hz,H-1’’),3.35(2H,q,J=7.0Hz,H-4),2.52-2.42(2H,m,H-2’’),2.36(2H,t,J=7.2Hz,H-2),1.87(2H,ap五重線,J=7.1Hz,H-3),1.25(3H,t,J=7.0Hz,CH3);13C NMR(125MHz,CDCl3,δ/ppm):173.2(C-1 or C-1’),168.9(C-1 or C-1’),70.5(C-2’),63.5(C-1’’),60.5(OCH2),38.3(C-4),31.7(C-2),31.4(t,J=21.7Hz,C-2’’),24.6(C-3),14.1(CH3),8個の炭素(7×CF2,1×CF3)は観測されず;19F NMR(282MHz,CDCl3,δ/ppm):-80.8(t,J=10.0Hz),-113.2(五重線,J=14.4Hz),-121.6,-121.9,-122.7,-123.6,-126.1,1個のフッ素は観測されず;IR(νmax,ニート,cm-1):3339(N-H),2938,1732(C=O),1666(C=O),1536,1446,1372,1348,1325,1235,1199,1144,1116,1029;HRMS(ESI+)m/z:C18H19F17NO4(M+H+)の計算値:636.1037,実測値:636.1041。
Rf=0.35(DCM-MeOH 90:10);1H NMR(500MHz,CDCl3,δ/ppm):4.12(2H,q,J=7.0Hz,OCH2),3.75(2H,t,J=6.8Hz,H-1’’),3.61(2H,t,J=5.0Hz,H-2’),3.35(1H,br s,NH),2.84(2H,t,J=5.0Hz,H-1’),2.73(2H,t,J=7.2Hz,H-4),2.47-2.38(2H,m,H-2’’),2.73(2H,t,J=7.2Hz,H-2),1.87(2H,ap五重線,J=7.2Hz,H-3),1.24(3H,t,J=7.0Hz,CH3);13C NMR(125MHz,CDCl3,δ/ppm):173.4(C-1),69.8(C-2’),62.9(C-1’’),60.4(OCH2),48.8(C-4 or C-1’),48.6(C-4 or C-1’),32.0(C-2),31.5(t,J=21.3Hz,C-2’’),24.6(C-3),14.1(CH3),8個の炭素(7×CF2,1×CF3)は観測されず;19F NMR(282MHz,CDCl3,δ/ppm):-80.8(t,J=9.9Hz),-113.4,-121.7,-121.9,-122.7,-123.6,-126.1,1個のフッ素は観測されず;IR(νmax,ニート,cm-1):3342(N-H),2935,1729(C=O),1656,1543,1444,1370,1348,1199,1145,1134,1016,1029;HRMS(ESI+)m/z:C18H20F17NNaO3(M+Na+)の計算値:644.1064,実測値:644.1066。
Rf=0.36(ヘキサン-EtOAc 80:20);1H NMR(500MHz,CDCl3,δ/ppm):5.63-5.59(2H,m,H-2とH-6),3.75-3.70(2H,m,H-1’’’),3.57(2H,br s,H-1’’or H-2’’),3.37(2H,br s,H-1’’or H-2’’),3.26(2H,br s,H-3’),2.46-2.33(2H,m,H-2’’’),1.86-1.58(10H,m,2CH2と2CH3),1.55-1.44(15H,m,2CH3とC(CH3)3);13C NMR(125MHz,CDCl3,δ/ppm):155.7(C(O)N),138.1(CqCH3),118.9(CH),80.3(C-4),79.4(C(CH3)3),69.8(CH2),62.9(C-1’’’),48.8(CH2),46.7(CH2),31.6(t,J=21.2Hz,C-2’’’),28.4(C(CH3)3),22.9(CH2),12.3(CH3),11.6(CH3),9個の炭素(1×CH2,7×CF2,1×CF3)は観測されず;19F NMR(282MHz,CDCl3,δ/ppm):-80.7(t,J=9.7Hz),-113.4,-121.7,-121.9,-122.7,-123.6,-126.1,1個のフッ素は観測されず;IR(νmax,ニート,cm-1):3449(O-H),2976,1674(C=O),1479,1416,1367,1237,1202,1170,1144,1006;HRMS(ESI+)m/z:C29H38F17NNaO4(M+Na+)の計算値:810.2422,実測値:810.2417。
Rf=0.74(ヘキサン-EtOAc 80:20);[α]D=+7.8(c=1.0,CHCl3);1H NMR(500MHz,CDCl3,δ/ppm):5.57(2H,q,J=6.2Hz,トランス-トランス異性体の2CH),5.43-5.27(2H,m,トランス-シス異性体の2CH),4.30(2H,br s,2NH),3.49-3.37(2H,m,2H-3’),1.96-1.51(30H,m,8CH3と2CH2と2H-1’’),1.43(18H,s,2C(CH3)3),1.39-1.16(4H,m,2CH2),0.91-0.85(12H,m,4H-2’’);13C NMR(125MHz,CDCl3,δ/ppm):156.2(C(O)),140.2(CqCH3),139.7(CqCH3),138.2(CqCH3),122.6(CH),122.5(CH),122.4(CH),118.1(CH),80.8(C(CH3)3),79.5(C-4),78.8(C-4),56.1(C-3’),36.3(CH2),34.3(CH2),32.5(CH2),28.4(C(CH3)3),27.0(CH2),26.6(CH2),23.5(CH2),22.8(CH3),19.2(CH2),17.8(CH2),14.8(CH3),14.7(CH3),14.4(CH3),13.2(CH3),12.6(CH3);HRMS(ESI+)m/z:C20H37NNaO3(M+Na+)の計算値:362.2666,実測値:362.2672。
中間体12:4-(3’-ジエチルアミノプロピル)-3,5-ジメチルヘプタ-2,5-ジエン-4-オール
Rf=0.39(DCM-MeOH 90:10);1H NMR(500MHz,CDCl3,δ/ppm):5.63(2H,q,J=6.7Hz,トランス-トランス異性体の2CH),5.59-5.55(1H,m,トランス-シス異性体のCH),5.38(1H,q,J=7.2Hz,トランス-シス異性体のCH),2.56-2.48(8H,m,4H-1’’),2.45-2.35(4H,m,2H-3’),2.04-1.87(4H,m,2CH2),1.78-1.73(4H,m,2CH2),1.64-1.46(24H,m,8CH3),1.04-0.99(12H,m,4H-2’’);13C NMR(125MHz,CDCl3,δ/ppm):139.9(CqCH3),139.3(CqCH3),122.5(トランス-シス異性体のCH),118.3(トランス-トランス異性体のCH),117.4(トランス-シス異性体のCH),79.7(C-4),79.0(C-4),54.4(C-3’),54.1(C-3’),45.8(C-1’’),45.6(C-1’’),37.5(C-1’),36.4(C-1’),23.7(CH3),21.8(CH2),21.6(CH2),14.8(CH3),14.2(CH3),13.4(CH3),13.2(CH3),12.6(CH3),10.5(C-2’’),10.2(C-2’’);IR(νmax,ニート,cm-1):3408(O-H),2970,2813,2813,1455,1377,1293,1195,1066;HRMS(ESI+)m/z:C16H32NO(M+H+)の計算値:254.2478,実測値:254.2484。
中間体13:N,N-ジエチル-3-(テトラメチルシクロペンタジエニル)プロパン-1-アミン
Rf=0.60(中和の酸化アルミニウム,DCM-MeOH 95:5);1H NMR(500MHz,CDCl3,δ/ppm):2.65-2.40(1H,m,CH),2.52(4H,q,J=7.3Hz,2H-1’),2.47-2.41(2H,m,H-1),2.35-2.11(2H,m,H-3),1.82-1.77(9H,m,3CH3),1.75-1.78(2H,m,H-2),1.05-0.96(9H,m,CH3と2H-2’);13C NMR(125MHz,CDCl3,δ/ppm):142.2(CqCH3),138.4(CqCH3),138.3(CqCH3),138.1(CqCH3),135.6(CqCH3),135.3(CqCH3),134.5(CqCH3),134.0(CqCH3),133.6(CqCH3),55.9(CH),53.4(CH2),53.1(CH2),52.7(CH2),52.0(CH2),51.5(CH),49.4(CH),46.9(C-1’),27.8(CH2),26.7(CH2),25.6(CH2),24.3(CH2),23.7(CH2),22.4(CH2),21.0(CH2),14.2(CH3),14.1(CH3),11.8(CH3),11.7(CH3),11.6(CH3),11.1(CH3),11.0(CH3);IR(νmax,ニート,cm-1):2968,2934,2870,2799,1742,1656,1445,1381,1294,1201,1070;HRMS(ESI+)m/z:C16H30N(M+H+)の計算値:236.2373,実測値:236.2376。
中間体14:N-Boc-4-(4’-アミノブチル)-3,5-ジメチル-ヘプタ-2,5-ジエン-4-オール
Rf=0.50(ヘキサン-EtOAc 70:30);1H NMR(500MHz,CDCl3,δ/ppm):5.57(2H,q,J=6.5Hz,トランス-トランス異性体の2CH),5.34(2H,dq,J=1.3,7.5Hz,トランス-シス異性体の2CH),4.54(2H,br s,2NH),3.12(4H,br s,2H-4’),1.84-1.71(6H,m,2H-1’と2OH),1.69-1.60(24H,m,8CH3),1.53-1.46(8H,m,4CH2),1.44(18H,s,2C(CH3)3);13C NMR(125MHz,CDCl3,δ/ppm):156.1(C(O)N),140.2(CqCH3),139.6(CqCH3),138.1(CqCH3),122.5(トランス-シス異性体のCH),122.4(トランス-シス異性体のCH),118.9(トランス-トランス異性体のCH),118.1(トランス-トランス異性体のCH),80.8(C(CH3)3),79.4(C-4),79.1(C-4),40.4(C-4’),39.4(C-1’),37.6(C-1’),28.4(C(CH3)3),23.4(CH3),22.8(CH3),20.7(CH2),20.5(CH2),14.8(CH3),14.4(CH3),13.4(CH3),13.2(CH3),12.6(CH3),12.4(CH3);IR(νmax,ニート,cm-1):3364(N-HとO-H),2975,2933,2865,1695(C=O),1515,1454,1366,1251,1172,1003;HRMS(ESI+)m/z:C18H33NNaO3(M+Na+)の計算値:334.2353,実測値:334.2357。
中間体15:(S)-tert-ブチル2-{(4E/Z)-3-[(2E)-ブタ-2-エン-2-イル]-3-ヒドロキシ-4-メチルヘキサ-4-エン-1-イル}ピロリジン-1-カルボキシレート
Rf=0.32(ヘキサン-EtOAc 80:20);[α]D=-30.5(c=1.0,CHCl3);1H NMR(500MHz,CDCl3,δ/ppm):5.61(2H,q,J=6.6,トランス-トランス異性体の2CH),5.40-5.31(2H,m,トランス-シス異性体の2CH),3.43-3.38(2H,m,2 NCH),3.36-3.31(4H,m,4NHCH2),1.93-1.77(10H,m,2×CH3と2×CH2),1.73-1.55(30H,m,10×CH3),1.35-1.25(4H,m,2×CH2);13C NMR(125MHz,CDCl3,δ/ppm):154.8,139.5,138.3,137.8,122.5,122.5,118.9,78.9,57.5,56.9,46.4,46.1,33.1,30.8,28.7,28.5,23.7,23.4,23.2,14.8,14.4,13.4,13.2,12.3(CqOHの1個の炭素シグナルが見えない);HRMS(ESI+)m/z:C20H35NNaO3(M+Na+)の計算値:360.2515,実測値:360.2509。
実施例1
RhCl2[η5:η1-C5(CH3)4(CH2)3N(CH2CH2OCH2CH2C8F17)H]
Rf=0.53(DCM-MeOH 97:3);mp 133.3-134.6℃(DCM-ヘキサン,v/v=1/2);1H NMR(500MHz,CDCl3,δ/ppm):3.85-3.76(1H,m,CH2),3.73-3.49(4H,m,2CH2),2.91-2.84(1H,m,CH2),2.79-2.67(2H,m,CH2),2.45-2.31(2H,m,H-2’’),2.25-1.91(4H,m,2CH2),1.76(3H,s,CH3),1.73(3H,s,CH3),1.67(3H,s,CH3),1.64(3H,s,CH3);13C NMR(125MHz,CDCl3,δ/ppm):103.0(d,J=7.5Hz,CqRh),94.3(d,J=8.8Hz,CqRh),93.2(d,J=8.0Hz,CqRh),92.0(d,J=9.1Hz,CqRh),85.1(d,J=9.6Hz,CqRh),69.0(C-3),62.7(CH2),50.7(CH2),48.3(CH2),31.4(t,J=21.2Hz,C-2’’),27.0(CH2),19.4(CH2),9.9(CH3),9.4(CH3),9.1(CH3),9.1(CH3),8個の炭素(7×CF2,1×CF3)は観測されず;19F NMR(282MHz,CDCl3,δ/ppm):-80.8(t,J=9.8Hz),-113.3,-121.6,-121.9,-122.7,-123.5,-126.1,1個のフッ素は観測されず;IR(νmax,ニート,cm-1):3272(N-H),2918,1487,1440,1370,1331,1243,1200,1145,1114,1006;HRMS(ESI+)m/z:C24H27F17 35ClNORh(M-Cl-,100%)の計算値:806.0559,実測値:806.0552,C24H27F17 37ClNORh(M-Cl-,35%)の計算値:808.0539,実測値:808.0533;C24H27Cl2F17NORhの元素分析計算値:C,34.22;H,3.23;N,1.66;実測値C,34.40;H,3.20;N,1.60。
[Rh{η5:η1-C5(CH3)4(CH2)3NH2}{CH3CN}2][SbF6]2
mp>250℃(MeCN);1H NMR(500MHz,DMSO,δ/ppm):4.22(2H,br s,NH2),2.59(2H,br s,H-3),2.17-2.11(2H,m,H-1),2.06-2.01(8H,m,H-2と2CH3CN),1.70(6H,s,2CH3),1.44(6H,s,2CH3);13C NMR(125MHz,DMSO,δ/ppm):119.0(C≡N),102.7-101.4(m,CqRh),86.1-85.2(m,CqRh),41.3(C-3),29.8(C-2),18.7(C-1),7.4(CH3),7.2(CH3),2.1(CH3CN),1個の炭素(CqRh)は観測されず;IR(νmax,ニート,cm-1):3328(N-H),3284(N-H),2321,2291,1594,1455,1370,1163,1083,1021;HRMS(ESI+)m/z:C12H20F6NRh121Sb(M-[SbF6 -]-2MeCN,100%)の計算値:515.9593,実測値:515.9588;C12H20F6NRh123Sb(M-[SbF6 -]-2MeCN,68%)の計算値:517.9598,実測値:517.9590;C16H26F12N3RhSb2の元素分析計算値:C,23.02;H,3.14;N,5.03;実測値C,23.20;H,3.10;N,4.90。
IrCl2[η5:η1-C5(CH3)4(CH2)3NH2]
Rf=0.67(DCM-MeOH 90:10);mp>250℃(DCM-ヘキサン,v/v=1/3);1H NMR(500MHz,CDCl3,δ/ppm):3.94(2H,br s,NH2),2.72-2.68(2H,m,H-3),2.18(2H,t,J=6.3Hz,H-1),1.96-1.91(2H,m,H-2),1.78(6H,s,2CH3),1.67(6H,s,2CH3);13C NMR(125MHz,CDCl3,δ/ppm):90.8(CqIr),88.7(CqIr),41.9(C-3),30.7(C-2),19.2(C-1),9.2(CH3),9.0(CH3),1個の炭素(CqIr)は観測されず;IR(νmax,ニート,cm-1):3234(N-H),3153(N-H),2948,2877,1593,1444,1376,1269,1240,1165,1083,1038;HRMS(ESI+)m/z:C12H20 35Cl191IrN(M-Cl-,50%)の計算値:404.0885,実測値:404.0883;C12H20 37Cl191IrNとC12H20 35Cl193IrN(M-Cl-,100%)の計算値:406.0900,実測値:406.0901;C13H22 37Cl193IrN(M-Cl-,26%)の計算値:408.0879,実測値:408.0878;C12H20Cl2IrNの元素分析計算値:C,32.65;H,4.57;N,3.17;Cl,16.06;実測値C,32.95;H,4.50;N,3.00,Cl,16.00。
IrCl2[η5:η1-C5(CH3)4(CH2)3N(CH3)H]
Rf=0.47(DCM-MeOH 90:10);mp 186.4-187.0℃(DCM-ヘキサン);1H NMR(500MHz,CDCl3,δ/ppm):4.22(1H,br s,NH),2.86-2.81(1H,m,HA-3),2.77-2.73(1H,m,HB-3),2.72(3H,d,J=6.0Hz,NCH3),2.24-2.17(1H,m,CH2),2.15-2.10(2H,m,CH2),2.00-1.93(1H,m,CH2),1.71(3H,s,CH3),1.70(3H,s,CH3),1.66(3H,s,CH3),1.64(3H,s,CH3);13C NMR(125MHz,CDCl3,δ/ppm):97.5(CqIr),85.7(CqIr),85.4(CqIr),53.3(C-3),39.6(NCH3),26.1(CH2),19.3(CH2),9.3(CH3),9.2(CH3),9.1(CH3),9.0(CH3),2個の炭素(CqIr)は観測されず;IR(νmax,ニート,cm-1):3178(N-H),2990,2970,2923,1738,1455,1374,1228,1217,1064,1028;HRMS(ESI+)m/z:C13H22 35Cl191IrN(M-Cl-,50%)の計算値:418.1041,実測値:418.1044;C13H22 37Cl191IrNとC13H22 35Cl193IrN(M-Cl-,100%)の計算値:420.1056,実測値:420.1052;C13H22 37Cl193IrN(M-Cl-,23%)の計算値:422.1035,実測値:422.1029;C13H22Cl2IrNの元素分析計算値:C,34.28;H,4.87;N,3.08;Cl,15.57;実測値C,34.40;H,4.80;N,3.00;Cl,15.30。
Ir2Cl4[η5-C5(CH3)4(CH2)3NMe2 HCl]2
1H NMR(500MHz,DMSO,δ/ppm):10.11(2H,br s,NH),3.11-3.08(4H,m,2H-3),2.72(12H,s,4NCH3),2.10(4H,t,J=8.3Hz,2H-1),1.84-1.79(4H,m,2H-2),1.70(12H,s,4CH3),1.64(12H,s,4CH3);13C NMR(125MHz,DMSO,δ/ppm):94.1(CqIr),92.1(CqIr),89.9(CqIr),56.1(C-3),42.0(NCH3),22.1(C-2),20.2(C-1),8.3(CH3),8.2(CH3);IR(νmax,ニート,cm-1):3011,1453,1406,1375,1031;HRMS(ESI+)m/z:C28H48 35Cl2 37Cl191Ir2N2とC28H48 35Cl3 191Ir193IrN2(M-[2HCl]-Cl-,63%)の計算値:901.2102,実測値:901.2112;C28H48 35Cl37Cl2 191Ir2N2,C28H48 35Cl2 37Cl191Ir193IrN2とC28H48 35Cl37Cl193Ir2N2(M-[2HCl]-Cl-,100%)の計算値:903.2106,実測値:903.2109;C28H48 37Cl3 191Ir2N2,C28H48 35Cl37Cl2 191Ir193IrN2とC28H48 35Cl2 37Cl193Ir2N2(M-[2HCl]-Cl-,65%)の計算値:905.2097,実測値:905.2102;C28H50Cl6Ir2N2の元素分析計算値:C,33.24;H,4.98;N,2.77;Cl,21.02;実測値C,33.10;H,4.90;N,2.60;Cl,20.60。
IrCl2[η5:η1-C5(CH3)4(CH2)3N(CH3)2]
Rf=0.90(DCM-MeOH 90:10);mp 198.3-199.5℃(DCM-ヘキサン,v/v=1/2);1H NMR(500MHz,CDCl3,δ/ppm):2.77(6H,s,2NCH3),2.60-2.58(2H,m,H-3),2.15-2.08(4H,m,2CH2),1.60(6H,s,2CH3),1.59(6H,s,2CH3);13C NMR(125MHz,CDCl3,δ/ppm):89.1(CqIr),84.7(CqIr),80.6(CqIr),64.2(C-3),52.7(NCH3),25.3(CH2),19.0(CH2),9.3(CH3),9.1(CH3);IR(νmax,ニート,cm-1):2917,1477,1448,1435,1375,1029,1002;HRMS(ESI+)m/z:C14H24 35Cl191IrN(M-Cl-,49%)の計算値:432.1198,実測値:432.1197;C14H24 37Cl191IrNとC14H24 35Cl193IrN(M-Cl-,100%)の計算値:434.1213,実測値:434.1215;C14H24 37Cl193IrN(M-Cl-,27%)の計算値:436.1195,実測値:436.1193;C14H24Cl2IrNの元素分析計算値:C,35.82;H,5.15;N,2.98;Cl,15.10;実測値C,36.20;H,5.15;N,2.90;Cl,14.75。
IrI2[η5:η1-C5(CH3)4(CH2)3NH2]
Rf=0.88(DCM-MeOH 90:10);mp>250℃(DCM);1H NMR(500MHz,CDCl3,δ/ppm):3.92(2H,br s,NH2),2.58-2.54(2H,m,H-3),2.20(2H,t,J=6.3Hz,H-1),2.05(6H,s,2CH3),1.92(6H,s,2CH3),1.85-1.81(2H,m,H-2);13C NMR(125MHz,CDCl3,δ/ppm):89.8(CqIr),89.7(CqIr),81.1(CqIr),42.5(C-3),29.1(C-2),19.3(C-1),12.2(CH3),10.1(CH3);IR(νmax,ニート,cm-1):3214(N-H),3139(N-H),2908,1579,1458,1371,1309,1262,1157,1070,1022;HRMS(ESI+)m/z:C12H20I191IrN(M-I-,64%)の計算値:496.0241,実測値:496.0237;C12H20I193IrN(M-I-,100%)の計算値:498.0264,実測値:498.0263;C12H20I2IrNの元素分析計算値:C,23.09;H,3.23;N,2.24;実測値C,23.55;H,3.30;N,2.20.Cについての元素分析データは範囲外(±0.4)であったが、現在までの最良値であった。
IrI2[η5:η1-C5(CH3)4(CH2)3N(CH3)2]
mp 203.0-204.7℃(CHCl3);1H NMR(500MHz,CDCl3,δ/ppm):3.13(6H,s,2NCH3),2.57(2H,br s,H-3),2.05(4H,s,2CH2),1.87(6H,s,2CH3),1.82(6H,s,2CH3);13C NMR(125MHz,CDCl3,δ/ppm):88.0(CqIr),86.7(CqIr),85.1(CqIr),64.9(C-3),58.9(NCH3),24.9(CH2),18.4(CH2),12.4(CH3),11.0(CH3);IR(νmax,ニート,cm-1):2906,1452,1439,1374,1364,1029;HRMS(ESI+)m/z:C14H24I191IrN(M-I-,54%)の計算値:524.0554,実測値:524.0551;C14H24I193IrN(M-I-,100%)の計算値:526.0578,実測値:526.0574;C14H24I2IrNの元素分析計算値:C,25.78;H,3.71;N,2.15;I,38.91;実測値C,26.15;H,3.70;N,2.00;I,38.45.Iについての元素分析データは範囲外(±0.4)であったが、現在までの最良値であった。
(R)-IrCl2[η5:η1-C5(CH3)4(CH2)2(CH(CH(CH3)2)NH2]
Rf=0.71(DCM-MeOH 95:5);[α]D=-12.18(c=1.0,CHCl3);mp 250.8-252.9℃(分解,DCM-ヘキサン,v/v=1/3);1H NMR(500MHz,CDCl3,δ/ppm):4.08(1H,br s,NH),3.27(1H,br s,NH),2.43-2.30(2H,m,H-3とHA-1),2.19-2.02(2H,m,HB-1とHA-2),1.94-1.82(1H,m,H-1’),1.78(3H,s,CH3),1.77(3H,s,CH3),1.69(6H,s,2CH3),1.57-1.42(1H,m,HB-2),0.98-0.95(6H,m,2H-2’);13C NMR(125MHz,CDCl3,δ/ppm):90.6(CqIr),90.2(CqIr),90.0(CqIr),59.2(C-3),33.4(C-2),33.3(C-1’),20.3(C-1),18.2(C-2’),18.1(C-2’),9.3(CH3),9.1(CH3),9.0(CH3),8.9(CH3),2個の炭素(CqIr)は観測されず;IR(νmax,ニート,cm-1):3299(N-H),3207(N-H),2962,2920,2876,1575,1478,1455,1369,1338,1282,1261,1186,1168,1102,1059,1034;HRMS(ESI+)m/z:C15H26 37Cl191IrNとC15H26 35Cl193IrN(M-Cl-,100%)の計算値:448.1369,実測値:448.1368;C15H26Cl2IrNの元素分析計算値:C,37.26;H,5.42;N,2.90;Cl,14.67;実測値C,37.60;H,5.40;N,2.80;Cl,14.40.
[Ir[η5:η1-C5(CH3)4(CH2)3NH2}{ビピリジル}][Cl]2
mp 197.6-199.2℃(分解,CHCl3);1H NMR(500MHz,MeOD,δ/ppm):8.92(2H,d,J=5.7Hz,2H-5’),8.65(2H,d,J=8.0Hz,2H-2’),8.30(2H,ap dt,J=8.0,1.4Hz,2H-3’),7.84(2H,ddd,J=8.0,5.7,1.3Hz,2H-4’),2.49-2.45(2H,m,H-3),2.44-2.41(2H,m,H-1),1.96-1.92(2H,m,H-2),1.80(6H,s,2CH3),1.41(6H,s,2CH3);13C NMR(125MHz,MeOD,δ/ppm):157.4(C-1’),153.6(C-5’),142.5(C-3’),130.6(C-4’),126.0(C-2’),101.2(CqIr),97.5(CqIr),80.3(CqIr),43.1(C-3),29.7(C-2),19.4(C-1),8.2(CH3),8.1(CH3);IR(νmax,ニート,cm-1):3448(N-H),3365(N-H),3116,3043,1698,1607,1472,1446,1314,1210,1162,1076,1033;HRMS(ESI+)m/z:C22H28 191IrN3(M-2Cl-,56%)の計算値:262.5939,実測値:262.5944;C22H28 193IrN3(M-2Cl-,100%)の計算値:263.5951,実測値:263.5960;C22H28Cl2IrN3・2H2Oの元素分析計算値:C,41.70;H,5.09;N,6.63;Cl,11.19;実測値C,41.60;H,5.40;N,6.20;Cl,11.20.Nについての元素分析データは範囲外(±0.4)であったが、現在までの最良値であった。
[Ir{η5:η1-C5(CH3)4(CH2)3NH2}{CH3CN}2][SbF6]2
mp>250℃(MeCN-Et2O,v/v=1/4);1H NMR(500MHz,CD3CN,δ/ppm):4.38(2H,br s,NH2),2.60-2.56(2H,m,H-3),2.30-2.25(2H,m,H-1),1.97(6H,s,2CH3CN),1.92-1.87(2H,m,H-2),1.86(6H,s,2CH3),1.65(6H,s,2CH3);13C NMR(125MHz,CD3CN,δ/ppm):100.6(CqIr),98.9(CqIr),81.4(CqIr),42.7(C-3),29.8(C-2),18.9(C-1),9.4(CH3),9.1(CH3),2個の炭素(C≡N及びCH3CN)は観測されず;IR(νmax,ニート,cm-1):3313(N-H),3274(N-H),2946,2315,1654,1597,1457,1365,1279,1191,1083,1030;HRMS(ESI+)m/z:C12H20F6N191Ir121Sb(M-[SbF6 -]-2MeCN,43%)の計算値:604.0139,実測値:604.0139;C12H20F6N191Ir123SbとC12H20F6N193Ir121Sb(M-[SbF6 -]-2MeCN,100%)の計算値:606.0156,実測値:606.0157;C12H20F6N193Ir123Sb(M-[SbF6 -]-2MeCN,53%)の計算値:608.0167,実測値:608.0164;C16H26F12N3IrSb2の元素分析計算値:C,20.80;H,2.84;N,4.55;実測値C,21.20;H,2.80;N,4.50。
Rh2Cl4[η5-C5(CH3)4(CH2)3NEt2 HCL]2
mp>250℃(MeOH);1H NMR(500MHz,DMSO,δ/ppm):10.14(2H,br s,2NH),3.09-3.06(12H,m,6NCH2),2.22(4H,t,J=8.3Hz,2H-1),1.84-1.80(4H,m,2H-2),1.70(12H,s,4CH3),1.63(12H,s,4CH3),1.19(12H,t,J=7.3Hz,4NCH2CH3);13C NMR(125MHz,DMSO,δ/ppm):100.1(d,J=8.8Hz,CqRh),99.1(d,J=7.5Hz,CqRh),97.9(d,J=8.0Hz,CqRh),50.2(NCH2),46.0(NCH2),21.4(C-2),20.5(C-1),8.6(CH3),8.4(CH3),1個の炭素(CH3)は観測されず;IR(νmax,ニート,cm-1):3214,3140,2933,2856,2756,2724,1581,1491,1453,1370,1355,1309,1263,1157,1114,1070,1023;C32H58Cl6N2Rh2の元素分析計算値:C,43.22;H,6.57;N,3.15;実測値C,43.65;H,6.35;N,2.90.Cについての元素分析データは範囲外(±0.4)であったが、現在までの最良値であった。
RhCl2[η5:η1-C5(CH3)4(CH2)3N(CH2CH3)H]
Rf=0.57(DCM-MeOH 90:10);mp 175.1-176.4℃(DCM);1H NMR(500MHz,CDCl3,δ/ppm):3.58-3.53(1H,m,HA-3),3.30(1H,br s,NH),2.84-2.73(2H,m,NCH2),2.68-2.61(1H,m,HB-3),2.19-1.99(4H,m,2CH2),1.77(3H,s,CH3),1.72(3H,s,CH3),1.67(3H,s,CH3),1.62(3H,s,CH3),1.10(3H,t,J=7.3Hz,CH3);13C NMR(125MHz,CDCl3,δ/ppm):105.1(d,J=7.5Hz,CqRh),94.8(d,J=8.8Hz,CqRh),93.1(d,J=8.8Hz,CqRh),90.1(d,J=7.5Hz,CqRh),83.8(d,J=8.8Hz,CqRh),45.3(NCH2),44.6(NCH2),26.0(C-2),19.3(C-1),13.7(CH3),9.9(CH3),9.4(CH3),9.3(CH3),9.2(CH3);IR(νmax,ニート,cm-1):3469(N-H),3217(N-H),2917,1651,1448,1374,1063,1028;HRMS(ESI+)m/z:C14H24 35ClNRh(M-Cl-,100%)の計算値:344.0640,実測値:344.0640。
Rh2Cl4[η5-C5(CH3)4(CH2)4NH3Cl]2
1H NMR(500MHz,DMSO,δ/ppm):8.05(6H,br s,2NH3),2.75(4H,br s,2H-4),2.15(4H,br s,2H-1),1.67(12H,s,4CH3),1.63-1.57(16H,m,2CH2と4CH3),1.48(4H,br s,2CH2);13C NMR(125MHz,DMSO,δ/ppm):99.4(d,J=7.5Hz,CqRh),99.3(d,J=7.5Hz,CqRh),99.1(d,J=7.5Hz,CqRh),38.3(C-4),26.9(CH2),23.9(CH2),22.7(C-1),8.7(CH3),8.6(CH3);IR(νmax,ニート,cm-1):3370(N-H),3100(N-H),2965,2914,1706,1591,1567,1479,1400,1367,1024;HRMS(ESI+)m/z:C26H44N2Rh2 35Cl3(M-[2HCl]-Cl-,100%)の計算値:695.0675,実測値:695.0673,C26H44N2Rh2 35Cl2 37Cl(M-[2HCl]-Cl-,100%)の計算値:697.0649,実測値:697.0647;C26H44N2Rh2 35Cl37Cl2(M-[2HCl]-Cl-,33%)の計算値:699.0627,実測値:699.0620。
RhCl2[η5:η1-C5(CH3)4(CH2)4NH2]
Rf=0.53(DCM-MeOH 90:10);1H NMR(500MHz,CDCl3,δ/ppm):3.23-3.19(2H,m,H-4),2.87(2H,br s,NH2),2.11-2.09(2H,m,CH2),2.07-2.01(2H,m,CH2),1.86-1.79(2H,m,CH2),1.66(6H,s,2CH3),1.64(6H,s,2CH3);13C NMR(125MHz,CDCl3,δ/ppm):100.9(d,J=11.3Hz,CqRh),96.7(d,J=10.0Hz,CqRh),89.3(d,J=10.0Hz,CqRh),43.9(C-4),28.9(CH2),22.9(CH2),21.5(CH2),9.7(CH3),9.0(CH3);HRMS(ESI+)m/z:C13H22NRh35Cl(M-Cl-,100%)の計算値:330.0490,実測値:330.0492,C13H22NRh37Cl(M-Cl-,33%)の計算値:332.0461,実測値:332.0457。
RhI2[η5:η1-C5(CH3)4(CH2)3NH2]
Rf=0.87(DCM-MeOH 90:10);mp>250℃(DCM-ヘキサン,v/v=1/2);1H NMR(500MHz,CDCl3,δ/ppm):3.17(2H,br s,NH2),2.56-2.53(2H,m,H-3),2.17-2.13(2H,m,H-1),2.14(6H,s,2CH3),2.00(6H,s,2CH3),1.94-1.89(2H,m,H-2);13C NMR(125MHz,CDCl3,δ/ppm):97.5(d,J=7.5Hz,CqRh),97.0(d,J=7.5Hz,CqRh),90.5(d,J=7.5Hz,CqRh),40.0(C-3),28.8(C-2),19.5(C-1),12.7(CH3),10.6(CH3);IR(νmax,ニート,cm-1):3223(N-H),3149(N-H),2942,2908,1580,1458,1370,1354,1145,1129,1015,924;HRMS(ESI+)m/z:C12H20NRhI(M-I-)の計算値:407.9690,実測値:407.9693;C12H20I2NRhの元素分析計算値:C,26.96;H,3.77;N,2.62;実測値C,27.50;H,3.80;N,2.50.Cについての元素分析データは範囲外(±0.4)であったが、現在までの最良値であった。
(R)-IrCl2[η5:η1-C5(CH3)4(CH2)2CH{CH2CH2CH2}NH]
Rf=0.51(DCM/MeOH,95:5).mp(分解)250.6-251.5℃(DCM-ヘキサン,v/v=1/3).1H NMR(500MHz,CDCl3,δ/ppm):(ジアステレオマーの混合物)4.59-4.57(1H,m,NH),3.78-3.72(1H,m,CH2),3.43-3.29(2H,m,CH2),3.12-3.07(1H,m,NCH),2.87-2.77(1H,m,CH2),2.66-2.58(1H,m,CH),2.41-1.78(14H,m,14CH2),1.73-1.71(24H,m,24CH3),1.53-1.46(2H,m,CH2)(1×NHシグナルが見えない);13C NMR(125MHz,CDCl3,δ/ppm):(ジアステレオマーの混合物)95.2(CqIr),93.0(CqIr),91.6(CqIr),89.9(CqIr),89.0(CqIr),88.6(CqIr),85.0(CqIr),81.9(CqIr),63.8(NCH),59.8(NCH),49.8(CH2),48.6(CH2),35.0(CH2),31.4(CH2),31.3(CH2),31.2(CH2),23.2(CH2),22.9(CH2),20.4(CH2),20.2(CH2),9.2(Cp*CH3),9.1(Cp*CH3),9.1(Cp*CH3),9.1(Cp*CH3),9.0(Cp*CH3),9.0(Cp*CH3),8.9(Cp*CH3),8.9(Cp*CH3),2個のCqIrが見えない.IR(νmax,ニート,cm-1):3427,3150,2959,2920,2854,1451,1368,700;HRMS(ESI+)m/z:C15H24 35Cl191IrN(M-Cl-,50%)の計算値:444.1204,実測値:444.1198;C15H24 37Cl191IrNとC15H24 35Cl193IrN(M-Cl-,100%)の計算値:446.1201,実測値:446.1213;C15H24 37Cl193IrN(M-Cl-,26%)の計算値:448.1197,実測値:448.1195;C15H24Cl2IrNの元素分析計算値:C,37.42%;H,5.02%;N,2.91%;実測値:C,37.00%;H,4.90%;N,2.80%。
[Ir{η5:η1-C5(CH3)4(CH2)3NH2}{2,4-ジフルオロ-N-フェニルピコリンアミド}][PF6]
1H NMR(500MHz,CD3OD,δ/ppm):8.80(1H,d,J=5.3Hz,H-4),8.27(1H,td,J=7.7,1.3Hz,H-6),8.15(1H,d,J=7.9Hz,H-7),7.86(1H,ddd,J=7.4,5.7,1.4Hz,H-5),7.41-7.12(2H,m,H-8,H-10),7.08(1H,br s,H-9),2.81(1H,br s,H-3),2.52-2.44(2H,m,H-3,H-1),2.24(1H,m,H-1),2.09(1H,m,H-2),1.88,(3H,s,CH3),1.85(1H,br s,H-2),1.57(3H,s,CH3),1.45(3H,s,CH3),0.89(3H,s,CH3);13C NMR(125MHz,CD3OD,δ/ppm):211.0(CO),154.5(Cq-Py),152.9(C-4),141.9(C-6),130.8(C-5),128.1(C-7),112.8(C-9),105.4(C-10),98.1(C-8),91.4(Cq-Ir),86.2(Cq-Ir),43.7(C-3),30.3(C-2),19.9(C-1),8.6(CH3),その他の炭素原子は観測されず;IR(vmax,ニート,cm-1):3589(N-H),3111(N-H),1629,1603,1501,840,557;HRMS(ESI+)m/z:C24H27F2 191IrN3O(M-PF6 -,60%)の計算値:602.1728,実測値:602.1722;C24H27F2 193IrN3O(M-PF6 -,100%)の計算値:604.1751,実測値:604.1749。
[Ir{η5:η1-C5(CH3)4(CH2)3NH2}{4-フルオロ-N-フェニル-2-メチルチオピコリンアミド}][PF6]2
1H NMR(500MHz,CD3OD,δ/ppm):8.14(1H,dd,J=7.9,1.1Hz,H-7),8.01(1H,t,J=7.8Hz,H-6),7.74(1H,dd,J=7.7,1.5Hz,H-5),7.17(4H,m,H-8-11),2.99(3H,s,CH3-4),2.82(1H,m,H-3),2.38(2H,m,H-3,H-1),2.17(1H,m,H-1),2.10(3H,s,CH3),2.01(1H,m,H-2),1.84(1H,m,H-2),1.61(3H,s,CH3),1.43(3H,s,CH3),1.36(3H,s,CH3);13C NMR(125MHz,CD3OD,δ/ppm):197.0(CS),163.6(Cq-F),140.8(C-6),129.1(C-5),124.7(C-7),123.3(C-8,C-11),116.6(C-9,C-10),91.1(Cq-Ir),88.5(Cq-Ir),88.0(Cq-Ir),81.9(Cq-Ir),44.7(C-3),30.5(C-2),29.9(CH3-4),20.0(C-1),10.7(CH3),9.4(CH3),9.1(CH3),8.3(CH3),その他の炭素原子は観測されず;IR(vmax,ニート,cm-1):3315(N-H),3271(N-H),3128,3044,1601,1543,1509,1470,1405,1237,1190,1162,1044,837,762,556;HRMS(ESI+)m/z:C25H30F191IrN3S(M-H-2PF6 -,60%)の計算値:614.1750,実測値:614.1737;C25H30F193IrN3S(M-H-2PF6 -,100%)の計算値:616.1774,実測値:616.1762。
[Ir{η5:η1-C5(CH3)4(CH2)3NH2}{dppm}][BF4]2
1H NMR(500MHz,CD3OD,δ/ppm):7.74(6H,m,Ph),7.67(6H,m,Ph),7.58(4H,m,Ph),7.38(4H,m,Ph),5.49(2H,s,H-4),2.69(2H,m,H-3),2.33(6H,t,J=4.0Hz,2CH3),2.23(2H,m,H-1),1.95(2H,m,H-2),1.26(6H,m,2CH3);13C NMR(125MHz,CD3OD,δ/ppm):134.6(Ph),133.5(Ph),133.1(Ph),131.7(Ph),130.9(Ph),99.3(Cq-Ir),54.9(C-4),42.4(C-3),26.0(C-2),19.9(C-1),10.7(CH3),9.1(CH3),その他の炭素原子は観測されず;31P NMR(121MHz,CD3OD,δ/ppm):-46.3;IR(vmax,ニート,cm-1):3391(N-H),1574,1437,1097,1058,721,699,650,621,541,508;HRMS(ESI+)m/z:C37H41 191IrNP2(M-H-2BF4 -,60%)の計算値:752.2320,実測値:752.2335;C37H41 193IrNP2(M-H-2BF4 -,100%)の計算値:754.2343,実測値:754.2341。
[IrCl{η5:η1-C5(CH3)4(CH2)3NH2}{ピリジン}][BF4]
1H NMR(500MHz,CD3OD,δ/ppm):8.83(2H,m,H-4),8.04(1H,tt,J=7.7,1.6Hz,H-6),7.61(2H,m,H-5),2.86(1H,m,H-3),2.60(1H,m,H-3),2.34(2H,m,H-1),2.05(2H,m,H-2),1.76(3H,s,CH3),1.66(3H,s,CH3),1.62(3H,s,CH3),1.15(3H,s,CH3);13C NMR(125MHz,CD3OD,δ/ppm):154.8(C-4),140.8(C-6),128.2(C-5),96.6(Cq-Ir),93.8(Cq-Ir),90.1(Cq-Ir),83.1(Cq-Ir),77.8(Cq-Ir),43.6(C-3),30.3(C-2),19.8(C-1),9.1(CH3),8.8(CH3),8.7(CH3),8.2(CH3);IR(vmax,ニート,cm-1):3276(N-H),3221(N-H),1579,1449,1058,1020,767,697,551,527,518;HRMS(ESI+)m/z:C12H20Cl191IrN(M-Py-BF4 -,60%)の計算値:404.0890,実測値:404.0879;C12H20Cl193IrN(M-Py-BF4 -,100%)の計算値:406.0914,実測値:406.0897。
イリジウム触媒を使用する基質の範囲
イリジウム錯体-溶媒耐性
Claims (14)
- 式(I)
Mは、イリジウムであり、
L1及びL2は、独立に、ハロゲン、ニトリル、アミン、ホスフィン、又は、5員若しくは6員の複素環から選択され、又はL1及びL2は、一緒になって、ジアミン、ジホスフィン、及び、置換又は非置換ビピリジンから選択される二座配位子であり、
ここで、L1基及びL2基は、非置換であり、又はハロ、C1~4アルキル、C1~4ハロアルキル、-ORA、-NRARB、-CN、-SO2RAで任意選択で置換されており、
R1は、Hであり、
R2は、H、メチル、エチル、フェニル、ベンジル、イソプロピル、又は、tert-ブチルを表し、
R 3及びR4は、それぞれ独立に、H、メチル、プロピル、イソプロピル、シクロプロピル、及び、tert-ブチルから選択され、
又はR3及びR4は、それらが結合している、共有の、隣接の又は非隣接の炭素原子と共に5員又は6員の炭素環を一緒に形成し、
又はR 2 と、R3及びR4のうちの1つとは、それらが結合している原子と一緒になって3~8員の複素環を形成し、
R5は、C 1~6アルキルであり、
pは、0又は1以上であり、
nは、2、3、又は4から選択され、
mは、0、1、2、3又は4から選択され、
RA 及びR B は、各出現において、独立に、H、C1~6アルキル又はC1~6ハロアルキルから選択される)
の金属錯体。 - pが、0である、請求項1に記載の金属錯体。
- 式(II):
Mは、イリジウムであり、
L1及びL2は、独立に、ハロゲン、ニトリル、アミン、ホスフィン、又は、5員若しくは6員の複素環から選択され、又はL1及びL2は、一緒になって、ジアミン、ジホスフィン、及び、置換又は非置換ビピリジンから選択される二座配位子であり、
ここで、L1基及びL2基は、非置換であり、又はハロ、C1~4アルキル、C1~4ハロアルキル、-ORA、-NRARB、-CN、-SO2RAで任意選択で置換されており、
R1は、Hであり、
R2は、H、メチル、エチル、フェニル、ベンジル、イソプロピル、又は、tert-ブチルを表し、
R 3及びR4は、それぞれ独立に、H、メチル、プロピル、イソプロピル、シクロプロピル、及び、tert-ブチルから選択され、
又はR3及びR4は、それらが結合している、共有の、隣接の又は非隣接の炭素原子と共に5員若しくは6員の炭素環を一緒に形成し、
又はR 2 と、R3及びR4のうちの1つとは、それらが結合している原子と一緒になって5~6員の複素環を形成し、
R5は、C 1~6アルキルであり、
pは、1以上であり、
nは、2、3、又は4から選択され、
mは、0、1、2、3又は4から選択され、
RA 及びR B は、各出現において、独立に、H、C1~6アルキル又はC1~6ハロアルキルから選択される)
による化合物であってもよい、金属錯体。 - Xが、任意の好適なモノアニオン性、ジアニオン性又はトリアニオン性の分子から選択される、請求項3に記載の金属錯体。
- pが、2である、請求項3に記載の金属錯体。
- Xが、水酸化物イオン、フッ化物イオン、塩化物イオン、臭化物イオン、ヨウ化物イオン、酢酸イオン、ギ酸イオン、フッ素酸イオン、亜フッ素酸イオン、臭素酸イオン、亜臭素酸イオン、ヨウ素酸イオン、亜ヨウ素酸イオン、塩素酸イオン、亜塩素酸イオン、炭酸水素イオン、次亜フッ素酸イオン、次亜塩素酸イオン、次亜臭素酸イオン、次亜ヨウ素酸イオン、過フッ素酸イオン、過塩素酸イオン、過臭素酸イオン、過ヨウ素酸イオン、クロム酸イオン、シアン酸イオン、シアン化物イオン、リン酸二水素イオン、亜リン酸二水素イオン、硝酸イオン、シュウ酸水素イオン、硫酸水素イオン、亜硫酸水素イオン、過マンガン酸イオン、亜硝酸イオン、チオシアン酸イオン、水素化物イオン、ヘキサフルオロリン酸イオン、ヘキサフルオロアンチモン酸イオン、テトラフルオロホウ酸イオン、過酸化物イオン、[B[3,5-(CF3)2C6H3]4]-、B(C6F5)4 -、Al(OC(CF3)3)4 -、硫酸イオン、亜硫酸イオン、硫化物イオン、過硫酸イオン、チオ硫酸イオン、次亜硫酸イオン、リン酸水素イオン、亜リン酸水素イオン、メタケイ酸イオン、炭酸イオン、過炭酸イオン、シュウ酸イオン、安息香酸イオン、酒石酸イオン、ホウ酸イオン、ホウ化物イオン、クエン酸イオン、次亜リン酸イオン、窒化物イオン、リン酸イオン、リン化物イオン及び亜リン酸イオンから選択され、任意選択でXが、フッ化物イオン、塩化物イオン、臭化物イオン、ヨウ化物イオン、ヘキサフルオロリン酸イオン、ヘキサフルオロアンチモン酸イオン若しくはテトラフルオロホウ酸イオンである、請求項3に記載の金属錯体。
- R5が、メチルである、請求項1~6のいずれか一項に記載の金属錯体。
- mが、0又は4である、請求項1~7のいずれか一項に記載の金属錯体。
- L1及びL2が、独立に、ハロ、C1~10アルキルニトリル、又は5員若しくは6員のヘテロアリール環から選択され、又はL1及びL2が、一緒になって、ビピリジン若しくはC1~10アルキルジホスフィンである、請求項1~8のいずれか一項に記載の金属錯体。
- R2が、メチルである、請求項1~9のいずれか一項に記載の金属錯体。
- nが、3である、請求項1~10のいずれか一項に記載の金属錯体。
- 請求項1~13のいずれか一項に記載の金属錯体を反応混合物に添加することを含む、触媒プロセス。
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US20180362566A1 (en) | 2018-12-20 |
EP3390421A1 (en) | 2018-10-24 |
WO2017103623A1 (en) | 2017-06-22 |
JP2019501165A (ja) | 2019-01-17 |
CN114405547A (zh) | 2022-04-29 |
JP2021098722A (ja) | 2021-07-01 |
CN108368145B (zh) | 2021-12-31 |
GB201522437D0 (en) | 2016-02-03 |
JP2023011693A (ja) | 2023-01-24 |
US10717754B2 (en) | 2020-07-21 |
EP3390421B1 (en) | 2020-01-29 |
KR20180095894A (ko) | 2018-08-28 |
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