JP6949903B2 - 光学活性ビスホスフィノメタン及びその製造方法、並びに遷移金属錯体及び不斉触媒 - Google Patents
光学活性ビスホスフィノメタン及びその製造方法、並びに遷移金属錯体及び不斉触媒 Download PDFInfo
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- JP6949903B2 JP6949903B2 JP2019116410A JP2019116410A JP6949903B2 JP 6949903 B2 JP6949903 B2 JP 6949903B2 JP 2019116410 A JP2019116410 A JP 2019116410A JP 2019116410 A JP2019116410 A JP 2019116410A JP 6949903 B2 JP6949903 B2 JP 6949903B2
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- optically active
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- bisphosphinomethane
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- reaction
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- 229910052723 transition metal Inorganic materials 0.000 title claims description 19
- 150000003624 transition metals Chemical class 0.000 title claims description 19
- 239000011982 enantioselective catalyst Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 48
- BWJRMVLPCQPWGR-UHFFFAOYSA-N boron;phosphane Chemical compound [B].P BWJRMVLPCQPWGR-UHFFFAOYSA-N 0.000 claims description 26
- 239000003446 ligand Substances 0.000 claims description 20
- PKPBCVSCCPTDIU-UHFFFAOYSA-N B.P Chemical class B.P PKPBCVSCCPTDIU-UHFFFAOYSA-N 0.000 claims description 16
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000004437 phosphorous atom Chemical group 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- LJDOJGHHINJZKE-UHFFFAOYSA-N B.OCP Chemical compound B.OCP LJDOJGHHINJZKE-UHFFFAOYSA-N 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- 229910000085 borane Inorganic materials 0.000 claims description 6
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000010948 rhodium Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 229910052703 rhodium Inorganic materials 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- -1 1,1,3,3-tetramethylbutyl group Chemical group 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 7
- 239000013256 coordination polymer Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 150000003216 pyrazines Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 238000011914 asymmetric synthesis Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012973 diazabicyclooctane Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- HMXQXVQEIZWUPS-UHFFFAOYSA-N B.C1C2CC3CC1CC(C2)(C3)PC12CC3CC(CC(C3)C1)C2 Chemical compound B.C1C2CC3CC1CC(C2)(C3)PC12CC3CC(CC(C3)C1)C2 HMXQXVQEIZWUPS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- UYAJYTUZKCAEHL-UHFFFAOYSA-N [Li].B.P Chemical compound [Li].B.P UYAJYTUZKCAEHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZBTYGZQHPMJJFS-UHFFFAOYSA-N tert-butyl(dimethyl)phosphane Chemical compound CP(C)C(C)(C)C ZBTYGZQHPMJJFS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PDVFSPNIEOYOQL-UHFFFAOYSA-N (4-methylphenyl)sulfonyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OS(=O)(=O)C1=CC=C(C)C=C1 PDVFSPNIEOYOQL-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- TWXBYZQOENIYHV-UHFFFAOYSA-N B(=O)OP(C)C(C)(C)C Chemical compound B(=O)OP(C)C(C)(C)C TWXBYZQOENIYHV-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFGWWRIJWASGEU-UHFFFAOYSA-N C12(CC3CC(CC(C1)C3)C2)C(P)C23CC1CC(CC(C2)C1)C3.B(=O)OP(C)C(C)(C)C Chemical compound C12(CC3CC(CC(C1)C3)C2)C(P)C23CC1CC(CC(C2)C1)C3.B(=O)OP(C)C(C)(C)C LFGWWRIJWASGEU-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000006579 Tsuji-Trost allylation reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- BLBBMBKUUHYSMI-UHFFFAOYSA-N furan-2,3,4,5-tetrol Chemical compound OC=1OC(O)=C(O)C=1O BLBBMBKUUHYSMI-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- IZDROVVXIHRYMH-UHFFFAOYSA-N methanesulfonic anhydride Chemical compound CS(=O)(=O)OS(C)(=O)=O IZDROVVXIHRYMH-UHFFFAOYSA-N 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PENAXHPKEVTBLF-UHFFFAOYSA-L palladium(2+);prop-1-ene;dichloride Chemical compound [Pd+]Cl.[Pd+]Cl.[CH2-]C=C.[CH2-]C=C PENAXHPKEVTBLF-UHFFFAOYSA-L 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5004—Acyclic saturated phosphines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
- C07B35/02—Reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5004—Acyclic saturated phosphines
- C07F9/5009—Acyclic saturated phosphines substituted by B, Si, P or a metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
- C07F15/0073—Rhodium 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
-
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Description
下記一般式(3)で表される光学活性ヒドロキシメチルホスフィンボランの水酸基を、脱離可能な官能基に変換した、下記一般式(4)で表される光学活性ホスフィンボラン誘導体の調製を行う第1工程、
前記リチオ化ホスフィンボランと前記一般式(4)で表される光学活性ホスフィンボラン誘導体とを反応させ、光学活性ビスホスフィノメタンボランを得る第2工程、
及び、前記光学活性ビスホスフィノメタンボランの脱ボラン化反応を行う第3工程を含む、前記第1の発明の光学活性ビスホスフィノメタンの製造方法である。
前記一般式(1)で表される本発明の光学活性ビスホスフィノメタンにおいて、R1はアダマンチル基である。
R1がアダマンチル基であることで、前記光学活性ビスホスフィノメタンは、室温で固体の性状となり、これを配位子として用いた遷移金属錯体を不斉触媒として用いた場合に高いエナンチオ選択性を示す。
R2が炭素数3以上の分岐アルキル基であることで、前記光学活性ビスホスフィノメタンを配位子として用いた遷移金属錯体は、不斉触媒として用いた場合に高い反応活性を示す。
(1)リチオ化ホスフィンボランの調製と、光学活性ホスフィンボラン誘導体の調製とを行う第1工程
(2)光学活性ビスホスフィノメタンボランを得る第2工程
(3)脱ボラン化反応を行う第3工程
以上のようにして、前記リチオ化ホスフィンボランは溶液として調製されるが、単離することなく、そのまま又は必要に応じて溶液濃度を調整して第2工程に用いることができる。
以上のようにして、前記一般式(4)で表される光学活性ホスフィンボラン誘導体は溶液として調製されるが、単離することなく、そのまま又は必要に応じて溶液濃度を調整して第2工程に用いることができる。
<(R)−tert−ブチル(ヒドロキシメチル)メチルホスフィンボラン(3a)>
[α]D27 −16.5(c1.0、AcOEt)
Rf=0.37(AcOEt/hexane=1:3)
1H−NMR(500MHz,CDCl3) δ 0.05−0.075(br s,3H),1.21(d,JHP=14.4Hz,9H),1.27(d,JHP=10.3Hz,3H),2.02(br s,1H),3.95(d,J=13.2Hz,1H),4.05(d,J=13.2Hz,1H)
13C−NMR(125MHz,CDCl3) δ 3.01(d,JCP=34.6Hz),25.4,27.2(d,JCP=32.2Hz),57.0(d,JCP=37.0Hz)
31P−NMR(202MHz,CDCl3) δ 28.2
以下のスキームに従って、(R)−ジ−1−アダマンチルホスフィノ(tert−ブチルメチルホスフィノ)メタン((R)−BulkyP*)を合成した。
三方コックとセプタムを装着した50mLの2口フラスコにジ−1−アダマンチルホスフィンボラン(1.581g、5mmol)を入れ、真空引きとアルゴン導入を繰り返して系内をアルゴン置換した。脱水THF(25mL)を加え、混合物を0℃に冷却し、n−BuLi(1.42Mヘキサン溶液、3.70mL、5.2mmol)を5分間かけて滴下した。滴下後、室温で30分間撹拌し、ジ−1−アダマンチルホスフィンボランのリチオ化物溶液(A液)を得た。
A液及びB液が入った二つのフラスコをカンヌールで連結し、A液を、B液の入ったフラスコに、約20分かけて滴下しながら移し入れた。約2時間かけて浴温を−30℃から室温まで上げ、さらに同温度で終夜撹拌を続けた。
反応混合物中の溶媒をエバポレーターで除去し、残渣に水(20mL)を加えてよく撹拌した後、ガラスフィルター(4G)を用いて吸引ろ過した。固形物を水(5mL×2回)とメタノール(3mL×2回)で洗浄し、真空乾燥して白色粉末を得た(1.75g)。この粗生成物をカラムクロマトグラフィー(和光ゲルC300、110g、ジクロロメタン:ヘキサン=3:1)で精製することにより(R)−ボラナート(tert−ブチルメチルホスフィノ)ボラナート(ジ−1−アダマンチル)ホスフィノメタン(5a)を得た(1.20g、収率54%)。分析結果を以下に示す。
[α]D24=−8.0(c1.02、CDCl3)
Rf=0.56(AcOEt/hexane=1:5)
1H−NMR(500MHz、CDCl3) δ 0.2−1.0(br m,6H),1.23(d,3JHP=13.8Hz,9H),1.57(d,2JHP=10.3Hz,3H),1.70−1.80(m,12H),1.82−1.90(m,2H),1.97−2.18(m,18H)
13C−NMR(125MHz,CDCl3) δ 6.1(dd,JCP=20.9,14.9Hz),6.6(d,JCP=32.2Hz),25.3,28.1−28.2(m),30.1(d,JCP=35.8Hz),36.4,36.5,37.6,37.8,37.9,38.9(d,JCP=22.7Hz)
31P−NMR(200MHz,CDCl3) δ 32.6,40.9
<第3工程>
三方コックとセプタムを装着した10mLの2口フラスコに(R)−ボラナート(tert−ブチルメチルホスフィノ)ボラナート(ジ−1−アダマンチル)ホスフィノメタン(223mg、0.5mmol)とDABCO(337mg、3mmol)を入れ、真空引きとアルゴン導入を繰り返して系内をアルゴン置換した。脱気トルエン(2.5mL)を加えた後、フラスコを80℃の油浴に浸し、マグネチックスターラーで撹拌しながら3時間反応させた。その後、フラスコを直接エバポレーターに連結して溶媒を除去した。メタノール4mLを加えて約10分間よく撹拌した後、固形物を3Gガラスフィルター上にろ取し、メタノール(3mL×2回)で洗浄した。さらに、酢酸エチルで洗浄(2mL×2回)した後、真空乾燥することにより(R)−ジ−1−アダマンチルホスフィノ(tert−ブチルメチルホスフィノ)メタン((R)−BulkyP*)を白色粉末として得た(195mg、収率93%)。分析結果を以下に示す。
Rf=0.85(AcOEt/hexane=1:5)
1H−NMR(500MHz,CDCl3) δ 1.02(d,2JHP=3.5Hz,3H),1.06(d,3JHP=11.5Hz,9H),1,55−1.62(m,2H),1.68−1.73(m,12H),1.82−1.87(m,6H),1.92−1.99(m,12H)
13C−NMR(125MHz,CDCl3) δ 7.1(dd,J=19.5,6.6Hz),11.4(dd,J=31.0,22.7Hz),26.6(d,J=13.1Hz),28.1(m),28.7(m),36.2(m),36.7(m),37.1,40.9(d,J=10.7Hz),41.3(dd,J=9.6,3.6Hz)
31P−NMR(202MHz,CDCl3) δ −13.2(d,JPP=114Hz),13.5(d,JPP=114Hz)
以下のスキームに従って、(R)−BulkyP*のロジウム錯体を合成した。
得られた生成物をアルゴン雰囲気下でジクロロメタン(0.50mL)に溶解し、この溶液にシリンジで酢酸エチル2.0mLを一挙に加えた。得られた均一溶液を冷蔵庫中で冷却し、析出した結晶をろ取し、ジクロロメタン/酢酸エチル(1:4)の混合溶媒で洗浄後、真空乾燥することにより橙色結晶の(R)−BulkyP*のロジウム錯体を得た(123mg、収率71%)。分析結果を以下に示す。
1H−NMR(500MHz,CDCl3) δ 1.18(d,3JHP=15.5Hz,9H),1.71(d,2JHP=8.6Hz,3H),1.73−2.20(m,30H),2.20−2.33(m,4H),2.38−2.54(m,4H),3.15−3.30(m,2H),5.07(br s,1H),5.11(br s,1H),5.69(br s,1H),5.79(br s,1H)
13C−NMR(125MHz,CDCl3) δ 9.3(d,J=20.3Hz),25.9(t,J=18.5Hz),26.6(d,J=3.6Hz),28.3(d,J=8.4Hz),28.4(d,J=8.4Hz),28.9,29.1,30.9,31.6,33.2(dd,J=17.3,4.1Hz),36.3,36.4,40.4,40.8,41.3(d,J=4.8Hz),43.4,91.0(m),91.7(m),97.4(m),100.7(m)
31P−NMR(202MHz,CDCl3) δ −14.6(dd,JPP=124Hz,JPRh=53Hz),−30.5(br d,JPP=124Hz)
<不斉水素化反応>
100mLの耐圧反応管に、実施例2で調製した(R)−BulkyP*のロジウム錯体(0.005mmol、4.3mg)、以下の式(a1)に示す基質を0.5mmol仕込んだ。反応管はステンレス製のチューブで水素ガスタンクに接続した。水素ガスで5回反応管を置換した後、1気圧の水素ガス(ジャパンファインプロダクツ製、99.99999%)を充填した。シリンジを用いて脱ガスした3mLのメタノールを耐圧反応管に添加した。次いで反応管内の水素ガスの圧力を3気圧にした(実施例3−5は1気圧)。表1に示す反応時間撹拌して水素化反応を実施した後、反応管に残存する水素を放出し、反応液をエバポレーターで濃縮して残渣を得た。残渣をフラッシュクロマトグラフィーで精製し(SiO2、酢酸エチル/ヘキサン、3:1)、式(a2)で表される生成物を得た。生成物の絶対配置及びee値は、保持時間と既報値との比較から決定した。結果を表1に示す。
なお、反応中、1価のロジウムイオンに(R)−BulkyP*が1:1で配位している金属錯体が形成されていることを、1H、13C、及び31Pの各NMR測定により確認した。
<不斉水素化反応>
100mLの耐圧反応管に、実施例2で調製した(R)−BulkyP*のロジウム錯体(0.005mmol、4.3mg)、以下の式(a3)に示す基質を0.5mmol仕込み、実施例3−1〜3−12と同様にして式(a4)で表される生成物を得た。生成物の絶対配置及びee値は、保持時間と既報値との比較から決定した。結果を表2に示す。
なお、反応中、1価のロジウムイオンに(R)−BulkyP*が1:1で配位している金属錯体が形成されていることを1H、13C、及び31Pの各NMR測定により確認した。
Claims (6)
- 一般式(1)の式中のR2がtert−ブチル基である、請求項1に記載の光学活性ビスホスフィノメタン。
- 下記一般式(2)で表されるホスフィンボランをリチオ化したリチオ化ホスフィンボランの調製と、
下記一般式(3)で表される光学活性ヒドロキシメチルホスフィンボランの水酸基を、脱離可能な官能基に変換した、下記一般式(4)で表される光学活性ホスフィンボラン誘導体の調製を行う第1工程、
前記リチオ化ホスフィンボランと前記一般式(4)で表される光学活性ホスフィンボラン誘導体とを反応させ、光学活性ビスホスフィノメタンボランを得る第2工程、
及び、前記光学活性ビスホスフィノメタンボランの脱ボラン化反応を行う第3工程を含む、請求項1記載の光学活性ビスホスフィノメタンの製造方法。 - 請求項1又は2に記載の光学活性ビスホスフィノメタンを配位子とする遷移金属錯体。
- 請求項4に記載の遷移金属錯体からなる不斉触媒。
- 請求項5に記載の不斉触媒を用いて不斉反応を行う工程を含む、有機化合物の製造方法。
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