CN109574946A - 二苯胺-胺-噁唑啉配体、合成方法及其金属配合物和用途 - Google Patents
二苯胺-胺-噁唑啉配体、合成方法及其金属配合物和用途 Download PDFInfo
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- CN109574946A CN109574946A CN201811512958.3A CN201811512958A CN109574946A CN 109574946 A CN109574946 A CN 109574946A CN 201811512958 A CN201811512958 A CN 201811512958A CN 109574946 A CN109574946 A CN 109574946A
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- Prior art keywords
- amine
- diphenylamines
- oxazoline
- ligand
- butyl
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- 239000003446 ligand Substances 0.000 title claims abstract description 43
- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- 150000004696 coordination complex Chemical class 0.000 title abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 150000002576 ketones Chemical class 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 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
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 claims abstract description 8
- 238000006276 transfer reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- -1 N-propyl Chemical group 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 230000008901 benefit Effects 0.000 claims description 4
- 229960004895 bretylium tosylate Drugs 0.000 claims description 4
- KVWNWTZZBKCOPM-UHFFFAOYSA-M bretylium tosylate Chemical group CC1=CC=C(S([O-])(=O)=O)C=C1.CC[N+](C)(C)CC1=CC=CC=C1Br KVWNWTZZBKCOPM-UHFFFAOYSA-M 0.000 claims description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001414 amino alcohols Chemical class 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 claims description 2
- 229960000655 ensulizole Drugs 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical group 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 125000002577 pseudohalo group Chemical group 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 238000006467 substitution reaction Methods 0.000 claims 2
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- YOCRKHKJFCWTHG-UHFFFAOYSA-N 2-[6-(4,5-dihydro-1,3-oxazol-2-yl)pyridin-2-yl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=N1 YOCRKHKJFCWTHG-UHFFFAOYSA-N 0.000 description 1
- VNJOEUSYAMPBAK-UHFFFAOYSA-N 2-methylbenzenesulfonic acid;hydrate Chemical compound O.CC1=CC=CC=C1S(O)(=O)=O VNJOEUSYAMPBAK-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical class [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D263/12—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals containing only hydrogen and carbon atoms
-
- 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
- B01J31/182—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 comprising aliphatic or saturated rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/20—Preparation of ethers by reactions not forming ether-oxygen bonds by hydrogenation of carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double 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
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
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Abstract
本发明提供的二苯胺‑胺‑噁唑啉配体,为式(1)所述的化合物或者为式(1)所述化合物的对映体或消旋体,其中,R1和R2分别独立为C1~C10的烃基、苄基、苯基或取代的苯基、杂芳基中的一种;R3为H或甲基。本发明同时公开了合成方法及其金属配合物和用途,以提供能够通过简单的合成线路实现高合成产率的催化剂,并确保其对烯烃和酮的不对称氢化和氢转移反应中具有非常高的催化活性。
Description
技术领域
本发明涉及催化剂技术领域,尤其涉及二苯胺-胺-噁唑啉配体、合成方法及其金属配合物和用途。
背景技术
过渡金属催化的不对称合成反应是制备手性化合物最为高效的方式之一,也是工业和学术界共同关注的热门领域。自从化学家们发现可以通过手性配体的结合来调节过渡金属在不对称催化反应中的活性和选择性之后,手性配体的设计就成为了过渡金属催化不对称合成领域的核心内容之一。至今已有数以千计的手性配体被发展出来应用于不对称合成反应,其中也涌现了一些具有广泛催化活性的优势手性配体[(a)Q.Zhou,PrivilegedChiral Ligands and Catalysts,Wiley-VCH,Weinheim,2011;b)T.P.Yoon,E.N.Jacobsen,Science 2003,299,1691;c)A.faltz,W.J.Drury III,PNAS2004,101,5723.]。手性噁唑啉可以由自然界常见的氨基酸来制备,是一类常见的手性配体砌块,如优势手性配体PyBox、BOX、PHOX等,可以和很多金属形成络合物催化许多类型的反应[(a)D.Rechavi,M.Lemaire,Chem.Rev.2002,102,346;(b)G.Desimoni,G.Faita,P.Quadrelli,Chem.Rev.2003,103,3119.]。因此,基于噁唑啉砌块构建不同的手性配体骨架引起了化学工作者的广泛兴趣,也由此实现了一些列高效的不对称催化转化,推动了不对称催化领域的发展[(a)S.Zhu,X.Song,Y.Li,Y.Cai,Q.Zhou,J.Am.Chem.Soc.2010,132,16374;(b)Y.Zhang,F.Wang,W.Zhang,J.Org.Chem.2007,72,9208;(c)B.Cheng,W.Liu,Z.Lu,J.Am.Chem.Soc.2018,140,501;(d)J.Guo,B.Cheng,X.Shen,Z.Lu,J.Am.Chem.Soc.2017,139,15316.]。
烯烃、酮等不饱和有机化合物的不对称氢化和氢转移等还原反应是高效的合成光学活性分子的手段,具有原子经济性高、操作简单、清洁绿色等优点,在化工工业大生产中有着重要的应用。现有的催化体系主要是基于铑、钌、铱、钯等铂族贵金属和手性膦配体的组合。铂族金属在地壳中储量较少(总计可开采储量为仅7.1万吨),属于战略性资源;同时手性膦配体的合成效率是一个难题。
因此,开发一种新的二苯胺-胺-噁唑啉配体,实现铁和钴等地球丰产过渡金属在不对称催化领域的广发应用,并进一步研究其高效合成的线路,不但具有迫切的研究价值,也具有良好的经济效益和工业应用潜力,这正是本发明得以完成的动力所在和基础。
发明内容
为了克服上述所指出的现有技术的缺陷,本发明人对此进行了深入研究,在付出了大量创造性劳动后,从而完成了本发明。
具体而言,本发明所要解决的技术问题是:提供二苯胺-胺-噁唑啉配体、合成方法及其金属配合物和用途,以提供能够通过简单的合成线路实现高合成产率的催化剂,并确保其对烯烃和酮的不对称氢化和氢转移反应中具有非常高的催化活性。
为解决上述技术问题,本发明的技术方案是:
第一方面,本发明提供了二苯胺-胺-噁唑啉配体,其为式(1)所述的化合物
或者为式(1)所述化合物的对映体或消旋体,其中,
R1和R2分别独立为C1~C10的烃基、苄基、苯基或取代的苯基、杂芳基;R3为H或甲基。
其中,所述的烃基为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、环戊基、正己基、环己基。
本发明中,作为一种优选的技术方案,R1优选为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基或苄基中的一种。
本发明中,作为一种优选的技术方案,R2优选为取代的苯基和环己基。其中,取代的苯基中取代基为C1~C6的烃基、烃氧基以及卤素,取代基数量为1-5。
第二方面,本发明提供了上述二苯胺-胺-噁唑啉配体的合成方法,包括如下步骤:
第一步:溶剂中,邻溴苯甲醛和胺在对甲苯磺酸(p-TsOH)的催化下缩合得到相应的亚胺,随后经氢化铝锂(LiAlH4)还原得到中间体—N-取代的邻溴苄胺(A);
第二步:溶剂中,邻氨基苯腈和手性胺基醇在三氟甲磺酸[Zn(OTf)2]的催化下缩合得到中间体—邻位噁唑啉取代的苯胺(B);
第三步:惰性气氛下,二氧六环溶剂中,邻溴苄胺(A)和苯胺(B)在醋酸钯的催化下偶联得到产物二苯胺-胺-噁唑啉配体(1)。
本发明中,作为作为一种优选的技术方案,第一步和第二步中的溶剂为甲苯溶剂。
本发明中,作为作为一种优选的技术方案,第三步中的溶剂为二氧六环溶剂。
其合成路线如下:
第三方面,本发明提供了二苯胺-胺-噁唑啉金属配合物,该配合物是由化合物1与元素周期表的过渡族的过渡金属形成,且具有如式(2)所述的通式
其中,M为过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os、Ir中的一种;
X选自卤化物(F、Cl、Br、I)、拟卤化物(氰化物、氰酸、盐、异氰酸盐)、羧酸、磺酸、膦酸的阴离子(碳酸根、甲酸根、乙酸根、丙酸根、甲基磺酸根、三氯甲基磺酸根、苯基磺酸根、甲苯磺酸根)中的任意一种;
E为H或甲基;
n1为X的个数,为0、1、2、3;
n2为E的个数,为0或1。
R1和R2分别独立为C1~C10的烃基、苄基、苯基或取代的苯基、杂芳基;R3为H或甲基。
其中,所述的烃基为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、环戊基、正己基、环己基。
本发明中,作为一种优选的技术方案,R1优选为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基或苄基中的一种。
本发明中,作为一种优选的技术方案,R2优选为取代的苯基和环己基。其中,取代的苯基中取代基为C1~C6的烃基、烃氧基以及卤素,取代基数量为1-5。
第四方面,本发明提供了二苯胺-胺-噁唑啉配体以及二苯胺-胺-噁唑啉金属配合物的用途,是指利用催化量的至少一种二苯胺-胺-噁唑啉配体或二苯胺-胺-噁唑啉金属配合物作为催化剂通过催化反应制备光学选择性有机化合物。例如可以以二苯胺-胺-噁唑啉金属配合物催化三取代烯烃的不对称氢化反应及酮的不对称氢转移反应。
采用了上述技术方案后,本发明的有益效果是:
本发明提供了一种新型二苯胺-胺-噁唑啉配体,二苯胺-胺-噁唑啉配体可以独立用于制备手性或非手性有机化合物,也可以与过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os、Ir形成稳定的金属配合物,该金属配合物能够应用于不对称催化反应,特别是对烯烃和酮的不对称氢化和氢转移反应中具有非常高的催化活性。本发明还提供了高效的合成路线,两步总产率均在80%以上。
本发明还提供了化合物1应用于金属催化不对称反应的用途,通过与金属预配位形成的金属催化剂或与金属盐现场生成金属催化剂,化合物1可以用于制备手性或非手性有机化合物。可根据本发明制备的手性或非手性有机化合物是活性物质或用于制备该物质的中间物,特别是在香料和增香剂、药物制剂、农用化学品的生产方面。
具体实施方式
下面结合具体的实施例对本发明进一步说明。但这些例举性实施方式的用途和目的仅用来例举本发明,并非对本发明的实际保护范围构成任何形式的任何限定,更非将本发明的保护范围局限于此。
二苯胺-胺-噁唑啉配体,其为式(1)所述的化合物
或者为式(1)所述化合物的对映体或消旋体,其中,R1和R2分别独立为C1~C10的烃基、苄基、苯基或取代的苯基、杂芳基;R3为H或甲基。
上述二苯胺-胺-噁唑啉配体的合成方法,包括如下步骤:
第一步:室温,反应瓶内依次加入邻溴苯甲醛(20mmol)、甲苯(30mL)、胺(22mmol)和甲苯磺酸一水合物(1mmol),升温至回流反应12小时;随后冷却至室温,硅藻土抽滤,滤液减压旋转蒸发除去溶剂得到相应的亚胺(黄色胶状物)。
另取一三口反应瓶,依次加入氢化铝锂(22mmol)、四氢呋喃(20mL),0℃、氮气氛下滴加亚胺/四氢呋喃(20mL)溶液,滴加结束后升温至回流反应12小时;
随后冷却至室温,缓慢滴加饱和氯化铵溶液猝灭反应,加入乙酸乙酯(20mL)和饱和食盐水(10mL),分液,水相再用乙酸乙酯萃取两次,合并有机相,无水硫酸钠干燥后减压旋转蒸发除去溶剂得到中间体A,反应方程式如下:
中间体A的检测结果如下:
无色油状液体,产率为92%。1H NMR:(500.1MHz,CDCl3)δ7.57(d,J=8.0Hz,1H),7.36(d,J=7.6Hz,1H),7.28-7.22(m,1H),7.17-7.10(m,1H),6.99(d,J=7.6Hz,1H),6.88-6.81(m,2H),4.20(s,2H),2.26(s,6H).
1H NMR:(500.1MHz,CDCl3)δ7.58(d,J=8.0Hz,1H),7.42(d,J=7.6Hz,1H),7.32-7.25(m,1H),7.19-7.04(m,4H),4.12(s,2H),3.43(br,1H),3.35-3.23(m,2H),1.21(d,J=7.0Hz,12H);
第二步:室温,反应瓶内依次加入邻氨基苯腈(10mmol)、甲苯(10mL)、手性胺基醇(11mmol)和三氟甲磺酸(1mmol),升温至回流反应24小时,冷却至室温,减压浓缩后柱层析分离得到中间体B,反应方程式为:
第三步:室温,惰性气氛下,反应瓶内依次加入中间体A(11mmol)、二氧六环(20mL)、中间体B(10mmol)、醋酸钯(0.5mmol)、双(2-二苯基磷苯基)醚(0.6mmol)和叔丁醇钠(15mmol),升温至回流反应24小时,冷却至室温,硅胶短柱抽滤,滤液减压浓缩后经柱层析分离得到产物二苯胺-胺-噁唑啉配体(1)。
采用如上的制备方法,根据原料的不同,选择R1、R2的种类,分别可以得到如下的二苯胺-胺-噁唑啉配体(1):
实施例1
采用如上的制备方法,选择R1、R2的种类,得到如下的二苯胺-胺-噁唑啉配体(1a),为白色固体,产率为88%。
检测结果如下:
1H NMR:(500.1MHz,CDCl3)δ10.39(br,1H),7.77(dd,J=8.0,1.6Hz,1H),7.47-7.38(m,2H),7.32-7.25(m,1H),7.24-7.07(m,7H),7.02(d,J=8.4Hz,1H),6.93(d,J=7.6Hz,2H),6.81-6.75(m,1H),6.75-6.69(m,1H),4.59-4.49(m,1H),4.28(dd,J=9.0,8.6Hz,1H),4.12-3.99(m,3H),3.01(dd,J=13.7,5.8Hz,1H),2.70(dd,J=13.7,8.2Hz,1H),2.18(s,6H);HRMS Calcd for[C31H31N3O+H]+:462.2540;found:462.2544.
实施例2
采用如上的制备方法,选择R1、R2的种类,得到如下的二苯胺-胺-噁唑啉配体(1b),为白色固体,产率为87%。
检测结果如下:
1H NMR:(399.9MHz,CDCl3)δ10.43(br,1H),7.78(dd,J=8.0,1.6Hz,1H),7.47(d,J=7.6Hz,1H),7.44(d,J=8.0Hz,1H),7.31-7.25(m,1H),7.24-7.17(m,1H),7.16-7.09(m,1H),7.01(d,J=8.4Hz,1H),6.94(d,J=7.6Hz,2H),6.83-6.75(m,1H),6.75-6.69(),4.38-4.28(m,1H),4.15(1,J=13.6Hz,2H),4.10-3.97(m,2H),3.35(br,1H),2.18(s,6H),1.78-1.65(m,1H),0.92(d,J=6.8Hz,3H),0.85(d,J=6.8Hz,3H);13C NMR:(125.8MHz,CDCl3)δ13C NMR:(125.8MHz,CDCl3)delta 163.7,146.8,146.0,139.6,134.9,131.9,130.0,129.9,129.8,128.6,128.0,124.3,124.2,122.0,116.6,113.0,110.2,72.9,68.8,49.0,33.0,18.9,18.5,18.3.HRMS Calcd for[C27H31N3O+H]+:414.2545;found:414.2550.
实施例3
采用如上的制备方法,选择R1、R2的种类,得到如下的二苯胺-胺-噁唑啉配体(1c),为白色固体,产率为88%。
检测结果如下:
1H NMR:(399.9MHz,CDCl3)δ10.41(s,1H),7.79(dd,J=7.8,1.6Hz,1H),7.57(dd,J=7.8,1.2Hz,1H),7.41(d,J=7.8Hz,1H),7.36-7.27(m,1H),7.24-7.16(m,2H),7.08-6.99(m,3H),6.94(d,J=8.4Hz,1H),6.75-6.68(m,1H),4.26(dd,J=9.6,8.4Hz,1H),4.13(dd,J=8.4,8.0Hz,1H),4.10-4.00(m,3H),3.31(br,1H),3.26-3.13(m,2H),1.11(d,J=7.0Hz,6H),1.07(d,J=7.0Hz,6H),0.85(s,9H);13C NMR:(125.8MHz,CDCl3)δ163.7,147.2,143.1,142.8,139.4,135.7,132.0,129.9,129.8,128.1,125.3,125.0,123.8,123.4,116.5,112.7,109.9,76.3,67.0,52.3,33.8,27.6,25.9,24.2,24.1;HRMS Calcd for[C32H41N3O+H]+:484.3328;found:484.3329.
实施例4
采用如上的制备方法,选择R1、R2的种类,得到如下的二苯胺-胺-噁唑啉配体(1d),为白色固体,产率为89%。
检测结果如下:
1H NMR:(399.9MHz,CDCl3)δ10.45(br,1H),7.78(dd,J=8.0,1.6Hz,1H),7.46(d,J=8.0Hz,1H),7.39(dd,J=7.6,1.2Hz,1H),7.32-7.25(m,1H),7.25-7.18(m,1H),7.12-7.06(m,1H),7.04(d,J=8.4Hz,1H),6.94(d,J=7.6Hz,2H),6.82-6.76(m,1H),6.76-6.69(m,1H),4.14(s,2H),4.00(s,2H),3.40(br,1H),2.20(s,6H),1.27(s,6H).HRMS Calcd for[C26H29N3O+H]+:400.2383;found:400.2388。
实施例5
二苯胺-胺-噁唑啉-铁配合物的合成
室温,氮气氛下,反应瓶内依次加入实施例1制备得到的二苯胺-胺-噁唑啉配体1a(1mmol),干燥四氢呋喃(THF)(5mL)和氯化亚铁(FeCl2)(0.95mmol),反应液逐渐变棕绿色悬浊液,搅拌反应5小时后抽滤,滤饼用乙醚洗涤三次(每次5mL),收集滤饼,油泵抽干得到棕绿色粉末状固体(2a),产率为88%。
检测结果如下:
Anal.Calcd for C31H31Cl2FeN3O:C,63.29;H,5.31;N,7.14;Found C,63.00;H,5.36;N,6.99.
实施例6
二苯胺-胺-噁唑啉-钴配合物的合成
室温,氮气氛下,反应瓶内依次加入实施例1制备得到的二苯胺-胺-噁唑啉配体1a(1mmol),干燥四氢呋喃(THF)(5mL)和氯化钴(CoCl2)(0.95mmol),反应液逐渐变绿色悬浊液,搅拌反应5小时后抽滤,滤饼用乙醚洗涤三次(每次5mL),收集滤饼,油泵抽干得到绿色粉末状固体(2b),产率为96%。
检测结果如下:
Anal.Calcd for C31H31Cl2CoN3O:C,62.95;H,5.28;N,7.10;Found C,62.88;H,5.11;N,6.92.
实施例7
二苯胺-胺-噁唑啉-锰配合物的合成
室温,氮气氛下,反应瓶内依次加入实施例1制备得到的二苯胺-胺-噁唑啉配体1a(1mmol),干燥四氢呋喃(THF)(5mL)和氯化锰(MnCl2)(0.95mmol),反应液逐渐变浅黄色悬浊液,搅拌反应5小时后抽滤,滤饼用乙醚洗涤三次(每次5mL),收集滤饼,油泵抽干得到黄白色粉末状固体(2c),产率为94%。
检测结果如下:
Anal.Calcd for C31H31Cl2MnN3O:C,63.38;H,5.32;N,7.15;Found C,62.99;H,5.01;N,6.96.
实施例8
二苯胺-胺-噁唑啉-锌配合物的合成
室温,氮气氛下,反应瓶内依次加入实施例1制备得到的二苯胺-胺-噁唑啉配体1a(1mmol),干燥四氢呋喃(THF)(5mL)和氯化锌(ZnCl2)(0.95mmol),反应液逐渐变白色悬浊液,搅拌反应5小时后抽滤,滤饼用乙醚洗涤三次(每次5mL),收集滤饼,油泵抽干得到白色粉末状固体(2d),产率为85%。
检测结果如下:
Anal.Calcd for C31H31Cl2ZnN3O:C,62.28;H,5.23;N,7.03;Found C,62.13;H,5.20;N,6.99.
实施例9
催化三取代烯烃的不对称氢化反应
室温,氮气氛下,在一干燥的反应试管中加入(手性)二苯胺-胺-噁唑啉-CoCl2配合物(2b)(0.005mmol),烯烃(0.5mmol),抽真空后反应管连接一个氢气球,随后注射加入干燥的甲苯(1mL)和三乙基硼氢化钠溶液(0.010mmol),室温下搅拌1小时后柱层析分离得到氢化产物。
检测结果如下:
无色油状液体,>99%产率,[α]20 D=25.8(c 0.86,CHCl3),95.2%ee;1H NMR:(400.1MHz,CDCl3)δ7.09(d,J=8.4Hz,2H),6.83(d,J=8.4Hz,2H),3.78(s,3H),2.60-2.48(m,1H),1.61-1.49(m,2H),1.21(d,J=7.0Hz,3H),0.81(t,J=7.4Hz,3H).
无色油状液体,>99%产率,[α]20 D=22.2(c 0.89,CHCl3),94.6%ee;1H NMR:(400.1MHz,CDCl3)δ7.14-7.03(m,4H),2.65-2.49(m,1H),2.31(s,3H),1.64-1.52(m,2H),1.22(d,J=6.8Hz,3H),0.82(t,J=7.2Hz,3H).
无色油状液体,>99%产率,[α]20 D=23.2(c 0.96,CHCl3),93.2%ee;1H NMR:(400.1MHz,CDCl3)δ7.32-7.23(m,2H),7.22-7.13(m,3H),2.72-2.59(m,1H),1.62-1.48(m,2H),1.34-1.08(m,7H),0.85(t,J=6.8Hz,3H).
无色油状液体,>99%产率,[α]20 D=19.4(c 1.01,CHCl3);95.0%ee;1H NMR:(400.1MHz,CDCl3)δ7.32-7.22(m,2H),7.22-7.11(m,3H),2.84-2.70(m,1H),1.58-1.31(m,3H),1.20(d,J=7.0Hz,3H),0.87(d,J=6.0Hz,3H),0.84(d,J=6.0Hz,3H).
实施例10
氯化钴催化三取代烯烃的氢化反应(对比实施例)
室温,氮气氛下,在一干燥的反应试管中加入CoCl(0.005mmol),烯烃(0.5mmol),抽真空后反应管连接一个氢气球,随后注射加入干燥的甲苯(1mL)和三乙基硼氢化钠溶液(0.010mmol),室温下搅拌1小时后气质联用检测未发现氢化产物。
实施例11
催化酮的不对称氢转移反应
室温,氮气氛下,在一干燥的反应试管中加入(手性)二苯胺-胺-噁唑啉-CoCl2配合物(2b)(0.005mmol),酮(0.5mmol),异丙醇(1mL)和叔丁醇钠(0.025mmol),然后在40℃下反应12小时后柱层析分离得到氢转移产物。
检测结果如下:
油状液体,98%产率,[α]20 D=+58.5(c 0.99,CHCl3);97.1%ee;1H NMR(CDCl3,400MHz):δ7.27-7.40(m,4H),7.24-7.30(m,1H),4.84-4.93(m,1H),1.93(br,1H),1.49(d,J=6.2Hz,3H).
油状液体,92%产率,[α]20 D=+55.4(c 1.01,CHCl3);97.7%ee;1H NMR(CDCl3,400MHz):δ7.27(d,J=7.8Hz,2H),7.16(d,J=7.8Hz,2H),4.82-4.92(m,1H),2.34(s,3H),1.79(br,1H),1.48(d,J=6.4Hz,3H).
油状液体,94%产率,[α]20 D=+17.5(c 1.1,CHCl3);97.5%ee;1H NMR(CDCl3,400MHz):δ7.30(d,J=7.8Hz,2H),6.88(d,J=7.8Hz,2H),4.82-4.91(m,1H),3.81(s,3H),1.73(br,1H),1.48(d,J=6.2Hz,3H).
油状液体,95%产率,[α]20 D=+35.5(c 1.01,CHCl3);96.6%ee;1H NMR(CDCl3,400MHz):δ7.27(d,J=7.6Hz,2H),7.12(d,J=7.0Hz,2H),4.80-4.90(m,1H),2.46(d,J=6.8Hz,2H),1.78-1.97(m,2H),1.44-1.53(m,3H),0.85-0.96(m,6H).
油状液体,89%产率,[α]20 D=+44.8(c 0.88,CHCl3);96.0%ee;1H NMR(CDCl3,400MHz):δ7.30-7.41(m,2H),7.03(t,J=8.6Hz,2H),4.81-4.92(m,1H),1.95(br,1H),1.47(d,J=6.4Hz,3H).
油状液体,97%产率,[α]20 D=+44.2(c 0.93,CHCl3);96.1%ee;1H NMR(CDCl3,400MHz):δ7.23-7.34(m,4H),4.79-4.87(m,1H),2.30(br,1H),1.44(d,J=6.4Hz,3H).
油状液体,97%产率,[α]20 D=+35.7(c 0.98,CHCl3);96.0%ee;1H NMR(CDCl3,400MHz):δ7.47(d,J=8.0Hz,2H),7.25(d,J=8.0Hz,2H),4.82-4.92(m,1H),1.84(br,1H),1.47(d,J=6.4Hz,3H).
实施例12
氯化钴催化酮的氢转移反应(对比实施例)
室温,氮气氛下,在一干燥的反应试管中加入CoCl2(0.005mmol),酮(0.5mmol),异丙醇(1mL)和叔丁醇钠(0.025mmol),然后在40℃下反应12小时气质联用检测未发现产物。
由以上实施例可知,采用本发明制备得到的二苯胺-胺-噁唑啉-CoCl2配合物能够有效催化烯烃或酮的不对称氢化和氢转移反应。
当理解,这些实施例的用途仅用于说明本发明而非意欲限制本发明的保护范围。此外,也应理解,在阅读了本发明的技术内容之后,本领域技术人员可以对本发明作各种改动、修改和/或变型,所有的这些等价形式同样落于本申请所附权利要求书所限定的保护范围之内。
Claims (10)
1.二苯胺-胺-噁唑啉配体,其特征在于:为式(1)所述的化合物
或者为式(1)所述化合物的对映体或消旋体,其中,
R1和R2分别独立为C1~C10的烃基、苄基、苯基或取代的苯基、杂芳基;R3为H或甲基。
2.如权利要求1所述的二苯胺-胺-噁唑啉配体,其特征在于:所述的烃基为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、环戊基、正己基、环己基。
3.如权利要求2所述的二苯胺-胺-噁唑啉配体,其特征在于:R1为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基或苄基中的一种。
4.如权利要求2所述的二苯胺-胺-噁唑啉配体,其特征在于:R2为取代的苯基和环己基。
5.二苯胺-胺-噁唑啉配体的合成方法,其特征在于:包括如下步骤:
第一步:溶剂中,邻溴苯甲醛和胺在对甲苯磺酸的催化下缩合得到相应的亚胺,随后经氢化铝锂还原得到中间体N-取代的邻溴苄胺(A);
第二步:溶剂中,邻氨基苯腈和手性胺基醇在三氟甲磺酸的催化下缩合得到中间体邻位噁唑啉取代的苯胺(B);
第三步:惰性气氛下,溶剂中,中间体—N-取代的邻溴苄胺(A)和邻位噁唑啉取代的苯胺(B)在醋酸钯的催化下偶联得到产物二苯胺-胺-噁唑啉配体(1)。
6.如权利要求5所述的合成方法,其特征在于:第一步和第二步中的溶剂为甲苯溶剂。
7.如权利要求5所述的合成方法,其特征在于:第三步中的溶剂为二氧六环溶剂。
8.二苯胺-胺-噁唑啉金属配合物,其特征在于:该配合物是权利要求1所述的化合物与元素周期表的过渡族的过渡金属形成,且具有如式(2)所述的通式
其中,M为过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os、Ir中的一种;
X选自卤化物(F、Cl、Br、I)、拟卤化物(氰化物、氰酸、盐、异氰酸盐)、羧酸、磺酸、膦酸的阴离子(碳酸根、甲酸根、乙酸根、丙酸根、甲基磺酸根、三氯甲基磺酸根、苯基磺酸根、甲苯磺酸根)中的任意一种;
E为H或甲基;
n1为X的个数,为0、1、2、3;
n2为E的个数,为0或1;
R1和R2分别独立为C1~C10的烃基、苄基、苯基或取代的苯基、杂芳基;R3为H或甲基。
9.二苯胺-胺-噁唑啉配体以及二苯胺-胺-噁唑啉金属配合物的用途,其特征在于:利用催化量的至少一种二苯胺-胺-噁唑啉配体或二苯胺-胺-噁唑啉金属配合物作为催化剂通过催化反应制备光学选择性有机化合物。
10.如权利要求9所述的用途,其特征在于:以二苯胺-胺-噁唑啉金属配合物催化三取代烯烃的不对称氢化反应及酮的不对称氢转移反应。
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