CN112824421A - 一种手性膦-亚磷酰胺酯配体及其制备方法和应用 - Google Patents
一种手性膦-亚磷酰胺酯配体及其制备方法和应用 Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 64
- KDPSKENBCWJPHJ-UHFFFAOYSA-N P.NP(O)O Chemical compound P.NP(O)O KDPSKENBCWJPHJ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 claims abstract description 41
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- -1 chlorophosphite ester Chemical class 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- PVHVYOCOWTWRMM-UHFFFAOYSA-N 2-(oxo-lambda5-phosphanylidyne)-1-phenylethanamine Chemical compound C1=CC=C(C=C1)C(C#P=O)N PVHVYOCOWTWRMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000005610 enamide group Chemical group 0.000 claims abstract description 7
- DQTRYXANLKJLPK-UHFFFAOYSA-N chlorophosphonous acid Chemical class OP(O)Cl DQTRYXANLKJLPK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004440 column chromatography Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
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- 239000005457 ice water Substances 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims description 33
- 125000001931 aliphatic group Chemical group 0.000 claims description 30
- 229910052717 sulfur Inorganic materials 0.000 claims description 30
- 230000003197 catalytic effect Effects 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 125000005842 heteroatom Chemical group 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000003708 ampul Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- CXBNMPMLFONTPO-UHFFFAOYSA-N acetic benzoic anhydride Chemical class CC(=O)OC(=O)C1=CC=CC=C1 CXBNMPMLFONTPO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000008365 aromatic ketones Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- GNNILMDCYQGMRH-UHFFFAOYSA-N formyl benzoate Chemical class O=COC(=O)C1=CC=CC=C1 GNNILMDCYQGMRH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 claims description 2
- 125000002015 acyclic group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 6
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- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- IGLMXMGJVVKOCT-UHFFFAOYSA-N N-(2-diphenylphosphoryl-1-phenylethyl)acetamide Chemical compound CC(=O)NC(CP(=O)(C1=CC=CC=C1)C2=CC=CC=C2)C3=CC=CC=C3 IGLMXMGJVVKOCT-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- TYSWGWOTWAKFQT-HXUWFJFHSA-N (1S)-2-diphenylphosphoryl-1-phenylethanamine Chemical compound C1=CC=C(C=C1)[C@@H](CP(=O)(C2=CC=CC=C2)C3=CC=CC=C3)N TYSWGWOTWAKFQT-HXUWFJFHSA-N 0.000 description 2
- HWCUCNKPBMGSSC-UHFFFAOYSA-N 1-phenylethenyl acetate Chemical compound CC(=O)OC(=C)C1=CC=CC=C1 HWCUCNKPBMGSSC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NPFDCQSGSMIQEN-XLNRJJMWSA-N N-[(Z)-2-diphenylphosphoryl-1-phenylethenyl]acetamide Chemical compound C1(=CC=CC=C1)P(=O)(C1=CC=CC=C1)\C=C(\C1=CC=CC=C1)/NC(C)=O NPFDCQSGSMIQEN-XLNRJJMWSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- SMWNFFKPVLVOQQ-UHFFFAOYSA-N methyl 2-acetamidoprop-2-enoate Chemical compound COC(=O)C(=C)NC(C)=O SMWNFFKPVLVOQQ-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- QKZWXPLBVCKXNQ-UHFFFAOYSA-N (2-methoxyphenyl)-[2-[(2-methoxyphenyl)-phenylphosphanyl]ethyl]-phenylphosphane Chemical compound COC1=CC=CC=C1P(C=1C=CC=CC=1)CCP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1 QKZWXPLBVCKXNQ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- XMHTUHZQDJLUSJ-UHFFFAOYSA-N Cl.OP(O)O Chemical compound Cl.OP(O)O XMHTUHZQDJLUSJ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- RWYYXMPWROIWLA-UHFFFAOYSA-N dimethyl 2-benzylbutanedioate Chemical compound COC(=O)CC(C(=O)OC)CC1=CC=CC=C1 RWYYXMPWROIWLA-UHFFFAOYSA-N 0.000 description 1
- NFOQJNGQQXICBY-UHFFFAOYSA-N dimethyl 2-methylbutanedioate Chemical compound COC(=O)CC(C)C(=O)OC NFOQJNGQQXICBY-UHFFFAOYSA-N 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- NUWGHZOGJFTJNN-UHFFFAOYSA-N methyl 2-acetamido-2-phenylpropanoate Chemical compound COC(=O)C(C)(NC(C)=O)C1=CC=CC=C1 NUWGHZOGJFTJNN-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
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- 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
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Abstract
本发明提供一种由手性β‑氨基膦中间体制备膦‑亚磷酰胺酯配体的方法及其在不对称反应中的应用。手性β‑氨基膦中间体通过(Z)‑(α‑芳基‑β‑磷酰基)烯酰胺的不对称氢化反应制得的手性N‑(2‑(磷酰基)‑1‑苯乙基)酰胺进而进行水解还原得到。将新制的氯代亚磷酸酯溶于甲苯中,按摩尔比手性膦胺化合物:氯代亚磷酸酯:三乙胺=1:1‑2:3‑5,于冰水浴中加入手性膦‑胺化合物和三乙胺溶于甲苯形成的溶液,将反应液升至18‑25℃搅拌反应10‑30小时,过滤,柱层析脱去溶剂、重结晶得到所需的膦‑亚磷酰胺酯配体。本发明的配体与金属前体形成的催化剂对C=C、C=N、C=O等双键的不对称氢化反应均可得到高达99%的对映选择性;催化剂活性高,TON高达10000。
Description
技术领域
本发明涉及一种基于手性β-氨基膦骨架的膦-亚磷酰胺酯配体及其制备方法。本发明还涉及上述配体在C=C、C=N、C=O等双键的不对称氢化反应中的应用。
背景技术
催化不对称氢化是不对称合成中的核心技术,是合成光学纯手性药物、农药、食品添加剂和香料的最有效方法之一,而手性配体的设计合成是实现这一核心技术的关键因素。不对称催化氢化反应,因其原子经济性高,一直备受人们关注,成为获得各手性化合物最直接、最有效的方法之一。在不对称催化氢化的发展过程中,手性膦配体的设计与合成占据着十分重要的地位[(a)Borner A. Phosphorus Ligands in Asymmetric Catalysis,Wiley-VCH,Weinheim,2008;(b) Zhou,Q.-L.Privileged Chiral Ligands andCatalysts,Wiley-VCH,Weinheim,2011.]。
20世纪70年代,DIOP和DIPAMP的成功,使得C2对称性的配体设计理念深入人心,人们发展了许多具有C2对称性的手性双膦配体[(c)Dang,T.P.;Kagan, H.B.J.Chem.Soc.,Chem.Commun.1971,481;(d)Vineyard,B.D.;Weinkauff,D.J. J.Am.Chem.Soc.1977,99,5946.];20世纪80年代,BINAP的兴起,逐步推动了轴手性配体的发展;20世纪90年代,随着Duphos和BPE配体的成功应用,环状膦配体的设计理念得到了大家的认可,一些环状的磷手性中心配体被相继报道 [(e)Berthod,M.;Lemaire,M.Chem.Rev.2005,105,1801;(f)Wang,C.-J.;Gao,F.J. Am.Chem.Soc.2008,130,17250;(g)Tang,W.;Chan,A.S.C.Angew.Chem.,Int. Ed.2009,48,9135.]。近来的研究表明非对称性杂化的手性膦配体在许多不对称催化反应中表现出与C2对称的手性双膦配体相当甚至更为优异的活性和光学选择性。这些非对称杂化的手性膦配体在不对称催化反应中的成功应用极大的拓展了手性膦配体的设计理念丰富了手性膦配体的种类。膦-亚磷酰胺配体代表了重要的一类非对称杂齿齿磷配体,在各种不对称转化中均显示出优异的结果。因此开发新的膦-亚磷酰胺酯配体具有重要的理论和现实意义。
发明内容
本发明公开了一种基于手性β-氨基膦骨架的膦-亚磷酰胺酯配体及其制备方法。
为实现上述目的,本发明提供的手性膦-亚磷酰胺酯配体,结构如下式:
式中:
Ar为苯基、2-取代、3-取代、4-取代、2,6-二取代、2,4,6-三取代的芳基等 C6-C60内的含或不含N、S、O、P等官能团的芳香基团。
X为手性或非手性的不含或含一个或多个N、S、O、P杂原子的脂肪基团;含一个或多个或不含N、S、O、P杂原子的芳香基团;手性或非手性的不含或含一个或多个N、S、O、P杂原子的联苯或联萘类芳香基团;或手性或非手性的螺环基团。主要包括:
R1为氢、C1-C40在内的脂肪基团,含有一个或多个N、S、O、P杂原子的脂肪基团;C7-C60的芳香基团与脂肪基的组合基团,含有一个或多个N、S、 O、P杂原子的C3-C60芳香基团与脂肪基的组合基团;C6-C60的芳香基团;或含有一个或多个N、S、O、P杂原子的杂环芳香基团。
所述的手性膦-亚磷酰胺酯配体,上述C1-C40的脂肪基团优选为烷基或环烷基。
所述的手性膦-亚磷酰胺酯配体,上述C6-C60的芳香基团优选为芳基。
所述的手性膦-亚磷酰胺酯配体,上述C7-C60的芳香基团与脂肪基的组合基团优选为苄基。
本发明提供了手性膦-亚磷酰胺酯配体的制备方法:
手性β-氨基膦化合物(即手性膦-胺化合物)通过(Z)-(α-芳基-β-磷酰基) 烯酰胺的不对称氢化反应制得的手性N-(2-(磷酰基)-1-苯乙基)酰胺进而进行水解还原得到。将新制的氯代亚磷酸酯溶于甲苯中,按摩尔比手性膦-胺化合物:氯代亚磷酸酯:三乙胺=1:1-2:3-5,于冰水浴中加入手性膦-胺化合物和三乙胺溶于甲苯形成的溶液,将反应液升至18-25℃搅拌反应10- 30小时,过滤,柱层析脱去溶剂、重结晶得到所需的膦-亚磷酰胺酯配体。
所述手性膦-胺化合物结构如下式:
式中:
Ar为苯基、2-取代、3-取代、4-取代、2,6-二取代、2,4,6-三取代的芳基等 C6-C60内的含或不含N、S、O、P等官能团的芳香基团。
R1为氢、C1-C40在内的脂肪基团,含有一个或多个N、S、O、P杂原子的脂肪基团;C7-C60的芳香基团与脂肪基的组合基团,含有一个或多个N、S、 O、P杂原子的C3-C60芳香基团与脂肪基的组合基团;C6-C60的芳香基团;或含有一个或多个N、S、O、P杂原子的杂环芳香基团。
所述手性膦-胺化合物的制备方法按以下路线合成:
式中:Ar为苯基、2-取代、3-取代、4-取代、2,6-二取代、2,4,6-三取代的芳基等C6-C60内的含或不含N、S、O、P等官能团的芳香基团;R2为氢、C1-C40在内的脂肪基团,含有一个或多个N、S、O、P杂原子的脂肪基团;C7-C60的芳香基团与脂肪基的组合基团,含有一个或多个含N、S、O、P杂原子的C3-C60芳香基团与脂肪基的组合基团;C6-C60的芳香基团;或含有一个或多个N、S、 O、P杂原子的杂环芳香基团。
手性N-(2-(磷酰基)-1-苯乙基)酰胺类化合物的制备:氮气保护下,将[Rh(COD)2]BF4金属前体与手性膦-亚磷酰胺酯配体[(Rc,Ra)-Me-PEAPhos]按摩尔比1.0∶0.5~1.0∶5.0在反应溶剂中搅拌0.5-2小时制的手性铑催化剂(手性铑催化剂的用量为1mol%)溶液转移至装有(Z)-(-芳基- -磷酰基)烯酰胺的安瓿瓶中,将安瓿瓶放入反应釜,用氢气置换三次后保持反应釜氢气压力为60bar。室温搅拌12-24小时;反应完毕后,减压旋蒸除去溶剂,柱层析分离,得到手性手性N-(2-(磷酰基)-1-苯乙基)酰胺类化合物;
手性N-(2-(磷酰基)-1-苯乙基)酰胺通过水解、还原方式高收率地得到立体构型保持的手性β-氨基膦化合物(即手性膦-胺化合物)。
本发明还涉及上述配体在C=C、C=N、C=O等双键的不对称氢化反应中的应用。
本发明提供的手性膦-亚磷酰胺酯配体可用于C=C、C=N、C=O键中不对称氢化反应中,将手性膦-亚磷酰胺酯配体与Pt、Pd、Ir、Ru或Rh按摩尔比1.1∶1-2.2∶1组成催化剂,反应底物与催化剂的比例为100-10000,反应时间0.1-24小时。
所述的不对称氢化反应为以下几类底物的催化不对称氢化反应:
(1)α-脱氢氨基酸的催化不对称氢化反应;
(2)β-脱氢氨基酸的催化不对称氢化反应;
(3)衣康酸酯及其β-取代的衣康酸酯类化合物的催化不对称氢化反应;
(4)α-非环状及环状烯酰胺的催化不对称氢化反应
(5)α-非环状及环状烯醇酯的催化不对称氢化反应;;
(6)α-乙酰氧基-β-取代丙烯酸酯的催化不对称氢化反应;
(7)苯或取代苯甲酰基甲酸酯类的催化不对称氢化;
(8)苯或取代苯甲酰基乙酸酯类的催化不对称氢化;
(9)取代或非取代芳香酮类化合物的催化不对称氢化;
(10)N-烷基和N-芳基亚胺的催化不对称氢化;
(11)N-酰基腙、磺酰亚胺和膦酰亚胺的催化不对称氢化;
(12)芳香和非芳香氮杂环的催化不对称氢化。
(13)(Z)-(α-芳基-β-膦酰基)烯酰胺的不对称氢化。
本发明的有益效果:
本发明的手性膦-亚磷酰胺酯配体与Pt、Pd、Ir、Ru或Rh等金属前体形成的催化剂性质稳定,对空气和湿度具有很好的忍耐力,其参与的不对称氢化反应条件温和,可以在室温下反应,氢气的压力适用范围广,从常压到高压均不影响催化剂的活性和立体选择性。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,应当理解,以下附图仅示出了本发明的某些实施例,因此不应被看作是对范围的限定,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他相关的附图。
图1手性膦-亚磷酰胺酯配体化合物L1的核磁氢谱图;
图2手性膦-亚磷酰胺酯配体化合物L1的核磁磷谱图;
图3产物N-(2-(二苯基磷酰基)-1-苯乙基)乙酰胺核磁共振氢谱图;
图4产物N-(2-(二苯基磷酰基)-1-苯乙基)乙酰胺核磁共振碳谱图;
图5产物N-(2-(二苯基磷酰基)-1-苯乙基)乙酰胺核磁共振磷谱图;
具体实施方式
一、手性配体的合成
本发明设计的手性配体是以(Z)-(α-芳基-β-膦酰基)烯酰胺为起始原料,通过不对称氢化,水解还原的方式得到手性β-氨基膦中间体,这也是该配体合成的关键步骤。手性β-氨基膦与亚磷酸酯氯化物缩合得到具有不同手性中心的膦-亚膦酰胺酯配体。
下面通过实施例详述本发明,但本发明并不限于下述实施例。核磁共振是通过Bruker核磁共振仪测定,高效液相色谱(HPLC)是通过Agilent 1100系列高效液相色谱测定。
实施例1
(a)
氮气保护下,将[Rh(COD)2]BF4(0.00125mmol,1mol%),手性膦-亚膦酰胺配体(0.001375mmol,1.1mol%)溶于二氯甲烷(1.0mL)中,室温(25℃)下搅拌1小时,加入底物(Z)-N-(2-(二苯基磷酰基)-1-苯基乙烯基)乙酰胺 (0.125mmol)的二氯甲烷(1.0mL)溶液,将其置于高压反应釜中,氢气置换 3次,然后通入60bar氢气,室温(25℃)下反应24小时。慢慢释放氢气,除去溶剂后用硅胶柱分离得到产物(S)-N-(2-(二苯基磷酰基)-1-苯乙基)乙酰胺。
将N-(2-(二苯基磷酰基)-1-苯乙基)乙酰胺1.05g(2.9mmol)溶于25ml 乙醇溶液中,搅拌加入6M盐酸溶液35ml,加热回流6小时。反应结束后缓慢加入饱和碳酸钠溶液至溶液呈碱性,用乙酸乙酯萃取分液、无水硫酸钠干燥,除去溶剂,得到目标产物(S)-2-(二苯基磷酰基)-1-苯基乙胺1g。产率98%。将(S)-2-(二苯基磷酰基)-1-苯基乙胺1.0g(3.1mmol)溶于20ml甲苯中,加入三乙胺18ml。0℃条件下滴加三氯硅烷6.3ml(15.3mmol),滴加完毕后密闭反应器中110℃条件下加热回流12小时。反应结束后加入20ml乙酸乙酯稀释,缓慢滴加饱和碳酸氢钠溶液至不再产生气泡为止。过滤除去白色固体,萃取分液,除去溶剂,经柱层析(乙酸乙酯:正己烷:甲醇=1:2:0.1)得到白色晶体0.9g。
(b)
按摩尔比手性二醇:PCl3:NMP(2-甲基吡咯烷酮)=1:5:0.01,将手性二醇与三氯化磷置于一反应瓶中加入催化量的2-甲基吡咯烷酮,加热回流反应至手性二醇完全溶解。减压脱去溶剂,加入甲苯真空干燥,再加入适量甲苯搅拌得到所需的氯代亚磷酸酯的甲苯溶液备用。
(c)
按摩尔比手性膦-胺化合物:氯代亚磷酸酯:Et3N(三乙胺)=1:1.2:3,将氯代亚磷酸酯溶于甲苯中,与0-5℃加入手性膦-胺化合物和三乙胺溶于甲苯形成的溶液,将反应液升至18-25℃搅拌反应10-30小时,柱层析得到得到所需的膦-亚磷酰胺酯配体,加入正己烷重结晶得到纯品L1,产率89%。化合物L1的核磁氢谱图和核磁磷谱图如图1和2所示。
实施例2
将实施例1中的手性膦-胺化合物改为下所示的中间体(m2),其余同实施例1,得到下所示手性膦-亚磷酰胺酯配体L2,产率80%。
实施例3
将实施例1中的手性膦-胺化合物改为下所示的中间体(m3),其余同实施例1,得到手性膦-亚磷酰胺酯配体L3,产率90%。
实施例4
将实施例1中的手性膦-胺化合物改为下所示的中间体(m4),其余同实施例1,得到下所示手性膦-亚磷酰胺酯配体L4,产率75%。
实施例5
将实施例1中的手性膦-胺化合物改为下所示的中间体(m5),其余同实例1,得到下所示手性膦-亚磷酰胺酯配体L5,产率78%。
实施例6
将实施例1中的手性二醇改为下所示化合物(n1),其余同实施例1,得到下所示手性膦-亚磷酰胺酯配体L6,产率86%。
二、不对称加氢反应
实施例7
氮气保护下,将[Rh(COD)2]BF4(0.00125mmol,1mol%),手性膦-亚膦酰胺配体(L1)(0.001375mmol,1.1mol%)溶于二氯甲烷(1.0mL)中,室温(25℃) 下搅拌1小时,加入底物(Z)-N-(2-(二苯基磷酰基)-1-苯基乙烯基)乙酰胺(0.125mmol)的二氯甲烷(1.0mL)溶液,将其置于高压反应釜中,氢气置换3次,然后通入60bar氢气,室温(25℃)下反应24小时。慢慢释放氢气,除去溶剂后用硅胶柱分离得到产物N-(2-(二苯基磷酰基)-1-苯乙基)乙酰胺。转化率99%,92%ee was determined by chiral HPLC(chiralcel AD-H, n-hexane/i-PrOH=65/35,0.8mL/min,254nm,40℃):tR(major)=8.64min,tR (minor)=9.5min.[α]D 29=13.93(c=2.31in CHCl3).1H NMR(400MHz,CDCl3)δ 7.82(s,1H),7.71(dd,J=11.1,7.5Hz,2H),7.58–7.46(m,4H),7.42(t,J=7.3Hz, 1H),7.33(t,J=6.3Hz,2H),7.22(d,J=7.4Hz,2H),7.15(t,J=7.3Hz,2H),7.08(t, J=7.1Hz,1H),5.30(s,1H),2.99–2.65(m,2H),1.99(s,2H).13C NMR(100 MHz,CDCl3)δ170.0,141.3(JC-p=9.3Hz),132.7,132.2(JC-p=2.5Hz),131.8(JC-p=1.2Hz),131.7,130.6,130.5,130.5,130.4,129.0(JC-p=11.6Hz),128.6(JC-p=12.3 Hz),128.5,127.4,126.1,49.8,35.7(JC-p=67.8Hz),23.2.31P NMR(162MHz, CDCl3)δ32.01(s).产物的核磁共振氢谱、碳谱和磷谱如图3、图4及图5所示。
实施例8
将实施例7中的氢气压力改为10bar,底物换为2-乙酰氨基丙烯酸甲酯,其余同实施例7,反应得手性乙酰氨基丙酸甲酯收率100%,对映选择性为99%。
实施例9
将实施例8中底物换成2-乙酰氨基肉桂酸甲酯,其余同实施例8,反应得产物得手性乙酰氨基苯丙酸甲酯转化率为99%,对映选择性为90%。
实施例10
将实施例8中的底物换成衣康酸二甲酯,其余同实施例8,反应得产物手性 2-甲基丁二酸二甲酯。转化率99%,对映选择性为99%。
实施例11
将实施例8中的底物改为β-苯基衣康酸二甲酯,其余同实施例8,反应得产物手性2-苯甲基丁二酸二甲酯。转化率99%,对映选择性为90%。
实施例12
将实施例8中的底物改为3-乙酰氨基-2-丁烯酸甲酯,其余同实施例8,反应得产物手性3-乙酰氨基-2-丁酸甲酯。转化率99%,对映选择性为98%。
实施例13
将实施例8中的底物改为α-乙酰氨基苯乙稀,其余同实施例8,反应得产物手性1-乙酰氨基苯乙烷。转化率99%,对映选择性为99%。
实施例14
将实施例8中的底物改为α-乙酰氧基苯乙稀,其余同实施例8,反应得产物手性α-乙酰氧基苯乙烷。转化率99%,对映选择性为90%。
Claims (10)
1.一种手性膦-亚磷酰胺酯配体,其特征在于:结构式如下:
式中:Ar为苯基、2-取代、3-取代、4-取代、2,6-二取代、2,4,6-三取代的芳基等C6-C60内的含或不含N、S、O、P等官能团的芳香基团;
X为手性或非手性的不含或含一个或多个N、S、O、P杂原子的脂肪基团;含一个或多个或不含N、S、O、P杂原子的芳香基团;手性或非手性的不含或含一个或多个N、S、O、P杂原子的联苯或联萘类芳香基团;或手性或非手性的螺环基团;
R1为氢、C1-C40在内的脂肪基团,含有一个或多个N、S、O、P杂原子的脂肪基团;C7-C60的芳香基团与脂肪基的组合基团,含有一个或多个N、S、O、P杂原子的C3-C60芳香基团与脂肪基的组合基团;C6-C60的芳香基团;或含有一个或多个N、S、O、P杂原子的杂环芳香基团。
2.根据权利要求1的手性膦-亚磷酰胺酯配体,其特征在于,所述C1-C40的脂肪基团为烷基或环烷基。
3.根据权利要求1的手性膦-亚磷酰胺酯配体,其特征在于,所述C6-C60的芳香基团为芳基。
4.根据权利要求1的手性膦-亚磷酰胺酯配体,其特征在于,所述C7-C60的芳香基团与脂肪基的组合基团为苄基。
5.一种如权利要求1所述手性膦-亚磷酰胺酯配体的制备方法,其特征在于:
(1)手性β-氨基膦化合物的制备:通过(Z)-(α-芳基-β-磷酰基)烯酰胺的不对称氢化反应制得的手性N-(2-(磷酰基)-1-苯乙基)酰胺进而进行水解还原得到手性β-氨基膦化合物,即手性膦-胺化合物;
(2)手性膦-亚磷酰胺酯配体的制备:将新制的氯代亚磷酸酯溶于甲苯中,然后于冰水浴中加入手性膦-胺化合物和三乙胺溶于甲苯形成的溶液,将反应液升至18-25℃搅拌反应10-30小时,过滤,柱层析脱去溶剂、重结晶得到所需的手性膦-亚磷酰胺酯配体;
所述手性膦-胺化合物:氯代亚磷酸酯:三乙胺的摩尔比为1:1-2:3–5。
8.根据权利要求5所述的手性膦-亚磷酰胺酯配体的制备方法,其特征在于:手性β-氨基膦化合物制备如下:
氮气保护下,将[Rh(COD)2]BF4金属前体与手性膦-亚磷酰胺酯配体[(Rc,Ra)-Me-PEAPhos]按摩尔比1.0:0.5~1.0:5.0在反应溶剂中搅拌0.5-2小时制备手性铑催化剂,手性铑催化剂溶液转移至装有(Z)-(-芳基-β-磷酰基)烯酰胺的安瓿瓶中,将安瓿瓶放入反应釜,用氢气置换三次后保持反应釜氢气压力为60bar;室温搅拌12-24小时;反应完毕后,减压旋蒸除去溶剂,柱层析分离,得到手性手性N-(2-(磷酰基)-1-苯乙基)酰胺类化合物;其中,手性铑催化剂的用量为1mol%;
手性N-(2-(磷酰基)-1-苯乙基)酰胺通过水解、还原方式高收率地得到立体构型保持的手性β-氨基膦化合物。
9.一种如权利要求1的手性膦-亚磷酰胺酯配体在对C=C、C=N、C=O双键的不对称氢化反应中的应用。
10.根据权利要求9所述的应用,其特征在于,所述的不对称氢化反应为以下几类底物的催化不对称氢化反应:
(1)α-脱氢氨基酸的催化不对称氢化反应;
(2)β-脱氢氨基酸的催化不对称氢化反应;
(3)衣康酸酯及其β-取代的衣康酸酯类化合物的催化不对称氢化反应;
(4)α-非环状及环状烯酰胺的催化不对称氢化反应
(5)α非环状及环状烯醇酯的催化不对称氢化反应;;
(6)α-乙酰氧基-β-取代丙烯酸酯的催化不对称氢化反应;
(7)苯或取代苯甲酰基甲酸酯类的催化不对称氢化;
(8)苯或取代苯甲酰基乙酸酯类的催化不对称氢化;
(9)取代或非取代芳香酮类化合物的催化不对称氢化;
(10)N-烷基和N-芳基亚胺的催化不对称氢化;
(11)N-酰基腙、磺酰亚胺和膦酰亚胺的催化不对称氢化;
(12)芳香和非芳香氮杂环的催化不对称氢化。
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