CN116715699A - 噁唑啉型手性n,p配体及其制备方法和应用 - Google Patents
噁唑啉型手性n,p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 80
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 80
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 74
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 43
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 39
- -1 aromatic ketone compounds Chemical class 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
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- 150000008365 aromatic ketones Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 claims description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000003017 phosphorus Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 claims 1
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- 239000002184 metal Substances 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 description 43
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 20
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
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- 238000003786 synthesis reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- APZBIEHZUCEYNW-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazol-2-ylmethanol Chemical class OCC1=NCCO1 APZBIEHZUCEYNW-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001414 amino alcohols Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- TZBCMHLFINVTGO-UHFFFAOYSA-N ethanol;naphthalene Chemical compound CCO.C1=CC=CC2=CC=CC=C21 TZBCMHLFINVTGO-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 4
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- 238000005086 pumping Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
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- 230000005311 nuclear magnetism Effects 0.000 description 3
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical group [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical group C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JZPDBTOWHLZQFC-UHFFFAOYSA-N chloro-di(propan-2-yl)phosphane Chemical compound CC(C)P(Cl)C(C)C JZPDBTOWHLZQFC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
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- 238000012544 monitoring process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
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- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CCHAJZURXPPHJU-UHFFFAOYSA-N 2-naphthalen-1-ylacetaldehyde Chemical compound C1=CC=C2C(CC=O)=CC=CC2=C1 CCHAJZURXPPHJU-UHFFFAOYSA-N 0.000 description 1
- BQKCABNKOFEHEG-UHFFFAOYSA-N 5H-dioxazole Chemical compound O1ON=CC1 BQKCABNKOFEHEG-UHFFFAOYSA-N 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical class ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000013557 residual solvent Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/653—Five-membered rings
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- 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
- B01J31/189—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 containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
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- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- B01J2531/72—Manganese
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
本发明属于金属有机配合物合成化学领域,具体涉及式(Ⅰ)所示噁唑啉型手性N,P配体及其制备方法和应用。式(Ⅰ)所示噁唑啉型手性N,P配体可制备噁唑啉型手性N,P配体锰配合物,制得的锰配合物结构简单,容易合成,且可以用于催化芳酮类化合物的不对称氢化反应,反应条件温和,拓宽了锰配合物的应用范围。
Description
技术领域
本发明属于金属有机配合物合成化学领域,具体涉及噁唑啉型手性N,P配体及其制备方法和应用。
背景技术
不对称催化因其高活性、低毒性以及高的原子经济性,在手性物质合成上具有重要应用价值。通过调控手性配体结构,可以高效率、高选择性的实现催化不同反应类型。新型手性配体的设计合成在不对称合成领域占据重要地位,目前已报道上千种手性配体及催化体系,并将其应用到不饱和有机物的氢化反应中。在众多的手性配体中,含氮配体具有易与金属形成配合物、高效、稳定等优点。但是这些催化体系主要以贵金属如Ru、Rh、Pd、Ir等。基于可持续发展和绿色催化的理念,近年来前过渡金属如Fe、Co、Ni等参与的催化转化迅速发展,极大丰富了催化研究领域,为替代贵金属试剂提供有效途径。相比之下锰系催化剂被应用于催化转化研究处于发展初期。因此,发展锰催化的不对称氢化反应以实现手性醇类精细有机化学品的高效合成具有重要意义。
发明内容
本发明的目的是在于提供一种噁唑啉型手性N,P配体,并用于制备噁唑啉型手性N,P配体锰配合物,所述噁唑啉型手性N,P配体锰配合物在不对称氢化反应种具有良好反应活性和选择性。
本发明的另一目的在于提供所述噁唑啉型手性N,P配体的制备方法。
本发明的另一目的在于提供所述噁唑啉型手性N,P配体在制备噁唑啉型手性N,P配体锰配合物中的应用。
本发明的另一目的在于提供所述噁唑啉型手性N,P配体锰配合物的制备方法。
为实现上述目的,本发明通过以下技术方案来实现的:
所述噁唑啉型手性N,P配体具有式(Ⅰ)结构:
所述R1选自苯基、异丙基、叔丁基;
R2选自异丙基、苯基、苄基;R3为氢。
进一步地,所述R1为异丙基,R2为异丙基。
所述噁唑啉型手性N,P配体的制备方法,包括如下步骤:
S1.制备2-羟甲基噁唑啉类化合物:采用式(Ⅳ)所示手性氨基醇类化合物和乙醇酸溶于溶剂,反应,经后处理得到式(Ⅴ)所示2-羟甲基噁唑啉类化合物;
S2.制备噁唑啉型手性N,P配体:采用步骤S1.制得的式(Ⅴ)所示2-羟甲基噁唑啉类化合物与二取代氯化磷(R1)2PCl在碱作用下,在溶剂中反应,经后处理得到式(Ⅰ)所示噁唑啉型手性N,P配体。
具体地,步骤S1.中,所述制备2-羟甲基噁唑啉类化合物的合成路线如下:
步骤S2.中,所述制备噁唑啉型手性N,P配体的合成路线如下:
进一步地,步骤S1.中,所述后处理为:
当R2为异丙基时,采用减压蒸馏进行提纯,减压蒸馏的温度为180℃;
当R2为苯基、苄基时,将体系冷却至室温,减压过滤、重结晶进行提纯,所述重结晶的溶剂体系为石油醚-乙酸乙酯或正己烷-乙酸乙酯。
进一步地,步骤S1.中,所述溶剂为四氢呋喃、二氯甲烷、氯苯、石油醚、正己烷或乙酸乙酯中的一种或几种。
进一步地,步骤S1.中,所述反应的时间为18~24小时。
进一步地,步骤S1.中,所述反应的温度为160℃。
进一步地,步骤S1.中,所述手性氨基醇类化合物和乙醇酸的摩尔比为1:1.1~1.5。
进一步地,步骤S2.中,当R1为叔丁基时,所述碱为1,8-二氮杂双环[5.4.0]十一碳-7-烯;
当R1为苯基、异丙基时,所述碱为三乙胺。
进一步地,步骤S2.中,所述溶剂为四氢呋喃。
进一步地,步骤S2.中,所述反应的时间为4~12小时。
进一步地,步骤S2.中,所述反应的温度为-40~室温。通常室温为25℃。
进一步地,步骤S2.中,所述二取代氯化磷:2-羟甲基噁唑啉类化合物:碱的摩尔比为1:1.05~1.2:1.05~12。
所述噁唑啉型手性N,P配体锰配合物具有式(Ⅱ)结构:
所述噁唑啉型手性N,P配体锰配合物的制备方法,包括如下步骤:
将上述噁唑啉型手性N,P配体和Mn(CO)5Br在惰性氛围下溶于溶剂,室温搅拌反应,经后处理得到噁唑啉型手性N,P配体锰配合物。
具体地,所述噁唑啉型手性N,P配体锰配合物合成路线如下:
进一步地,所述溶剂为四氢呋喃。
进一步地,所述反应的时间为12~24小时。
进一步地,所述噁唑啉型手性N,P配体和Mn(CO)5Br的摩尔比为1:1.1~1.5。
进一步地,所述后处理为采用针头滤器过滤,真空除去溶剂,采用正己烷洗涤,真空除去残留溶剂得到噁唑啉型手性N,P配体锰配合物。
本发明的另一目的在于提供所述噁唑啉型手性N,P配体锰配合物在作为芳酮类化合物的不对称氢化反应催化剂中的应用。
进一步地,所述芳酮类化合物具有式(Ⅲ)结构:
所述R4选自甲基、硝基、甲氧基、苯基、氰基或卤素中的一种;所述R5选自甲基或苯基。
具体地,所述噁唑啉型手性N,P配体锰配合物用于芳酮类化合物的不对称氢化反应的步骤如下:
将噁唑啉型手性N,P配体锰配合物、式(Ⅲ)所示芳酮类化合物和硅烷在惰性氛围下置于甲苯中,室温搅拌反应,经后处理得到式(Ⅵ)所示手性醇;
具体地,式(Ⅵ)所示手性醇合成路线如下:
进一步地,所述硅烷为苯基硅烷。
进一步地,所述反应的时间为12~24小时。
进一步地,所述噁唑啉型手性N,P配体锰配合物、芳酮类化合物和硅烷的摩尔比为1:50~100:50~100。
进一步地,所述后处理为采用乙酸乙酯进行萃取并采用柱层析提纯后旋蒸得手性醇。
进一步地,所述柱层析中采用的淋洗剂为体积比10:1的石油醚和乙酸乙酯。
与现有技术相比,本发明具有如下有益效果:
本发明提供噁唑啉型手性N,P配体和制备方法,具有简便、高效和易合成的特点,同时丰富了N,P配体的类型,且为金属配合物构筑及催化剂的发展提供了选择;所述噁唑啉型手性N,P配体可以制备噁唑啉型手性N,P配体锰配合物,制得的锰配合物结构简单,容易合成,且可以用于催化芳酮类化合物的不对称氢化反应,反应条件温和。
附图说明
图1为噁唑啉型手性N,P配体锰配合物合成方法路线图;
图2为实施例1中异丙基取代的2-羟甲基噁唑啉的核磁氢谱;
图3为实施例1中异丙基取代的2-羟甲基噁唑啉的核磁碳谱;
图4为实施例1中噁唑啉型手性N,P配体的核磁氢谱;
图5为实施例1中噁唑啉型手性N,P配体的核磁碳谱;
图6为实施例1中噁唑啉型手性N,P配体的核磁磷谱;
图7为实施例2中苯基取代的2-羟甲基噁唑啉的核磁氢谱;
图8为实施例2中苯基取代的2-羟甲基噁唑啉的核磁碳谱;
图9为实施例2中噁唑啉型手性N,P配体的核磁氢谱;
图10为实施例2中噁唑啉型手性N,P配体的核磁磷谱;
图11为实施例3中苄基取代的2-羟甲基噁唑啉的核磁氢谱;
图12为实施例3中苄基取代的2-羟甲基噁唑啉的核磁碳谱;
图13为实施例3中噁唑啉型手性N,P配体的核磁氢谱;
图14为实施例3中噁唑啉型手性N,P配体的核磁磷谱;
图15为实施例4制得的噁唑啉型手性N,P配体锰配合物的核磁氢谱;
图16为实施例4制得的噁唑啉型手性N,P配体锰配合物的核磁碳谱;
图17为实施例4制得的噁唑啉型手性N,P配体锰配合物的核磁磷谱;
图18为实施例4制得的噁唑啉型手性N,P配体锰配合物的单晶结构图;
图19为实施例5制得的萘乙醇的核磁氢谱;
图20为实施例5制得的萘乙醇的核磁碳谱;
图21为实施例5制得的苯乙醇的核磁氢谱;
图22为实施例5制得的苯乙醇的核磁碳谱。
具体实施方式
下面结合具体实施例对本发明做出进一步地详细阐述,所述实施例只用于解释本发明,并非用于限定本发明的范围。下述实施例中所使用的试验方法如无特殊说明,均为常规方法;所使用的材料、试剂等,如无特殊说明,为可从商业途径得到的试剂和材料。
实施例1
噁唑啉型手性N,P配体,结构如下:
上述结构的噁唑啉型手性N,P配体制备方法如下:
S1.称取异丙基取代手性氨基醇(5.15g,0.05mol)和乙醇酸(4.56g,0.06mol,1.2eq)溶解于氯苯(60mL)中,装上回流冷凝管和分水器。在160℃下,搅拌反应18小时。在180℃减压蒸馏得到白色固体即为异丙基取代的2-羟甲基噁唑啉,产率62%。其核磁氢谱和核磁碳谱如图2和图3所示。
从图2中得出核磁氢谱数据如下:1H NMR(400MHz,C6D6)δ5.42(br,1H),4.25(m,2H),3.81–3.66(m,1H),3.62–3.49(m,2H),1.46(pd,J=6.8,5.5Hz,1H),0.82(d,J=6.7Hz,3H),0.67(d,J=6.8Hz,3H).
从图3中得出核磁碳谱数据如下:13C{1H}NMR(101MHz,C6D6)δ168.86,71.54,70.69,57.05,32.59,18.45,18.10.
S2.称取步骤S1.制备的异丙基取代的2-羟甲基噁唑啉(150mg,1.05mmol),溶于四氢呋喃中,逐滴滴加三乙胺(1.22g,12mmol),搅拌均匀后,继续逐滴加入氯二异丙基膦(152mg,1mol),迅速产生白色沉淀,搅拌反应过夜。通过核磁监测反应,反应结束后,硅藻土过滤,滤液抽干得到无色液体。产率92%。核磁氢谱、核磁碳谱和核磁磷谱如图4~图6所示。
从图4中得出核磁氢谱数据如下:1H NMR(400MHz,C6D6)δ4.43(dd,J=9.4,1.0Hz,2H),3.80(td,J=7.2,1.3Hz,1H),3.68–3.54(m,2H),1.68(dtt,J=14.2,7.1,1.7Hz,2H),1.49(dq,J=13.4,6.7Hz,1H),1.16(ddd,J=10.4,7.0,1.5Hz,6H),1.00(ddd,J=15.5,7.2,1.9Hz,6H),0.91(d,J=6.7Hz,3H),0.72(d,J=6.7Hz,3H).
从图5中得出核磁碳谱数据如下:13C{1H}NMR(101MHz,C6D6)δ163.62,72.33,70.03,66.87,66.64,32.76,28.31,28.30,28.14,28.12,18.48,18.31,17.71,17.51,16.79,16.77,16.70,16.68.
从图6中得出核磁磷谱数据如下:31P{1H}NMR(162MHz,C6D6)δ161.45.
实施例2
上述结构的噁唑啉型手性N,P配体的制备方法如下:
S1.称取苯基取代手性氨基醇(6.85g,0.05mol)和乙醇酸(4.56g,0.06mol,1.2eq)溶解于氯苯(60mL)中,装上回流冷凝管和分水器。在160℃下,搅拌反应18小时。反应结束后冷却至室温,产物会以固体形式析出。过滤,并使用乙酸乙酯/石油醚混合溶剂重结晶,得到白色粉状固体,即为苯基取代的2-羟甲基噁唑啉。产率86%。其核磁氢谱和核磁碳谱如图7和8所示。
从图7中得出核磁氢谱数据如下:1H NMR(400MHz,MeOD)δ7.39–7.33(m,4H),7.27(m,1H),5.05(dd,J=6.7,5.2Hz,1H),4.05(d,J=3.3Hz,2H),3.81(dd,J=6.0,3.4Hz,2H),3.33(br,1H).
从图8中得出核磁碳谱数据如下:13C{1H}NMR(101MHz,MeOD)δ173.46,139.63,128.10,127.05,126.52,64.63,61.30,54.94.
S2.称取步骤S1.制备苯基取代的2-羟甲基噁唑啉(114.5mg,1.05mmol),溶于四氢呋喃中,逐滴滴加三乙胺(1.22g,12mmol),搅拌均匀后,继续逐滴加入氯二异丙基膦(152mg,1mol),迅速产生白色沉淀,搅拌反应过夜。通过核磁监测反应,反应结束后,硅藻土过滤,滤液抽干得到白色固体。产率92%。核磁氢谱和核磁磷谱如图9和10所示。
核磁氢谱数据如下:1H NMR(400MHz,Chloroform-d)δ7.36–7.25(m,5H),5.58(t,J=0.9Hz,1H),4.66(d,J=4.6Hz,2H),3.96–3.89(m,2H),2.01(s,2H),1.22(t,J=12.5Hz,12H).
核磁碳谱数据如下:13C{1H}NMR(101MHz,Chloroform-d)δ153.21,138.61,128.92,128.60,128.58,69.03,68.97,65.84,34.71,19.20.
核磁磷谱数据如下:31P{1H}NMR(162MHz,Chloroform-d)δ165.35.
实施例3
噁唑啉型手性N,P配体,结构如下:
上述结构的噁唑啉型手性N,P配体的制备方法如下:
步骤和参数同实施例2,区别在于,步骤S1.中采用等摩尔的苄基取代手性氨基醇替换苯基取代手性氨基醇,得到白色固体,即苄基取代的2-羟甲基噁唑啉。产率82%。其核磁氢谱和核磁碳谱如图11和图12所示。
从图11中得出核磁氢谱数据如下:1H NMR(400MHz,MeOD)δ7.35–7.17(m,5H),4.18(td,J=7.5,3.9Hz,1H),3.99–3.86(m,2H),3.57(d,J=5.0Hz,2H),3.33(br,1H),2.94(dd,J=13.7,6.6Hz,1H),2.81(dd,J=13.7,7.9Hz,1H).
从图12中得出核磁碳谱数据如下:13C{1H}NMR(101MHz,MeOD)δ173.43,138.19,128.94,127.99,125.99,62.34,61.11,52.18,36.59.
制得的噁唑啉型手性N,P配体的产率为94%。核磁氢谱和核磁磷谱如图13和14所示。
核磁氢谱数据如下:1H NMR(500MHz,Chloroform-d)δ7.30–6.97(m,5H),4.27(d,J=2.4Hz,2H),4.26–4.21(m,2H),4.12(d,J=12.5Hz,1H),3.23(dt,J=12.4,1.0Hz,1H),2.73(dt,J=12.5,1.0Hz,1H),2.01(s,2H),1.22(d,J=25.1Hz,12H).
核磁碳谱数据如下:13C{1H}NMR(101MHz,Chloroform-d)δ160.00,136.18,129.27,129.20,128.63,70.20,66.96,65.11,35.77,34.40,19.20.
核磁磷谱数据如下:31P{1H}NMR(162MHz,Chloroform-d)δ167.61.
实施例4
将实施例1制得噁唑啉型手性N,P配体(0.5mmol),金属锰前体Mn(CO)5Br(151.2mg,0.55mmol),溶于THF(10mL)中,室温搅拌反应过夜。使用核磁检测跟踪反应进程,待原料反应完全后,静置。反应液通过针头滤芯过滤,抽干滤液得到黄色粘稠液体,使用正己烷多次洗涤,转移出洗涤液,抽干得到噁唑啉型手性N,P配体锰配合物,简称Mn-1,结构如下:
实施例4制得的噁唑啉型手性N,P配体锰配合物的核磁氢谱、核磁碳谱和核磁磷谱如图15~17所示,单晶结构图如图18所示,晶体数据如表1所示:
从图15得出核磁氢谱数据如下:1H NMR(400MHz,C6D6)δ4.48(ddd,J=15.7,8.5,1.3Hz,1H),4.09–4.01(m,1H),3.87(dd,J=23.8,15.7Hz,1H),3.63(dp,J=10.1,7.2Hz,1H),3.47(dd,J=9.0,6.4Hz,1H),3.39–3.32(m,1H),2.57(dtt,J=10.2,6.8,3.3Hz,1H),2.36(dp,J=14.3,7.2Hz,1H),1.35(dd,J=16.2,7.4Hz,3H),1.13(ddd,J=18.3,15.6,7.1Hz,6H),0.95(dd,J=11.2,7.1Hz,3H),0.48(d,J=6.8Hz,3H),0.40(d,J=7.0Hz,3H).
从图16中得出核磁碳谱数据如下:13C{1H}NMR(101MHz,C6D6)δ169.32,169.28,76.40,76.37,67.52,59.54,59.50,28.52,28.44,28.40,28.19,27.93,18.04,17.23,17.18,16.78,16.69,15.77,15.73,13.03.
从图17中得出核磁磷谱数据如下:31P{1H}NMR(162MHz,C6D6)δ185.15.
表1实施例4制得的制得的噁唑啉型手性N,P配体锰配合物的晶体结构数据
实施例5催化反应
(1)将实施例4制得的噁唑啉型手性N,P配体锰配合物用于催化芳酮类化合物的不对称氢化反应,具体如下:于手套箱中称取萘乙酮(170mg,1mmol),苯硅烷(108mg,1mmol),置于圆底烧瓶中,加入2mol%的实施例10制得的噁唑啉型手性N,P配体锰配合物(10.7mg,0.02mmol),以甲苯为溶剂,室温搅拌反应36小时。通过TLC监测反应,待反应结束后,使用乙酸乙酯进行萃取。加入柱层析硅胶,旋蒸除去溶剂,采用柱层析进行目标产物分离。使用石油醚和乙酸乙酯为淋洗剂(石油醚:乙酸乙酯=10:1),收集含有产物的洗脱液,减压除去溶剂得产物,即萘乙醇。产率80%。对映体过量百分数利用OD-3手性柱经高效液相色谱分析得出ee值为92%。流动相为正己烷和异丙醇(体积比为95:5),流动速率为1mL/min,光源波长为220nm,保留时间分别为tR=18.2min(minor),tR=19.2min(major)。萘乙醇的核磁氢谱和核磁碳谱如图19和20所示。
由图19得核磁氢谱数据如下:1H NMR(400MHz,CDCl3)δ7.79–7.72(m,4H),7.47–7.39(m,3H),4.96(q,J=6.5Hz,1H),2.34(s,1H),1.51(d,J=6.5Hz,3H).
由图20得核磁碳谱数据如下:13C{1H}NMR(101MHz,CDCl3)δ143.3,133.4,132.9,128.3,128.0,127.7,126.2,125.8,123.9,123.8,70.5,25.2.
(2)将实施例4制得的噁唑啉型手性N,P配体锰配合物用于催化芳酮类化合物的不对称氢化反应,具体如下:于手套箱中称取苯乙酮(120mg,1mmol),苯硅烷(108mg,1mmol),置于圆底烧瓶中,加入2mol%的实施例10制得的噁唑啉型手性N,P配体锰配合物(10.7mg,0.02mmol),以甲苯为溶剂,室温搅拌反应36小时。通过TLC监测反应,待反应结束后,使用乙酸乙酯进行萃取。加入柱层析硅胶,旋蒸除去溶剂,采用柱层析进行目标产物分离。使用石油醚和乙酸乙酯为淋洗剂(石油醚:乙酸乙酯=10:1),收集含有产物的洗脱液,减压除去溶剂得产物,即苯乙醇。产率85%。对映体过量百分数利用OD-3手性柱经高效液相色谱分析得出ee值为83%。流动相为正己烷和异丙醇(体积比为95:5),流动速率为1mL/min,光源波长为220nm,保留时间分别为tR=10.2min(minor),tR=11.2min(major)。苯乙醇的核磁氢谱和核磁碳谱如图21和22所示。
由图21得核磁氢谱数据如下:1H NMR(400MHz,Chloroform-d)δ7.35–7.23(m,5H),4.83(qt,J=6.5,1.5Hz,1H),1.45(d,J=6.5Hz,3H).
由图22得核磁碳谱数据如下:13C{1H}NMR(101MHz,Chloroform-d)δ145.9,128.5,127.4,125.4,70.3,25.2.
本发明制得的噁唑啉型手性N,P配体锰配合物用于催化芳酮类化合物的不对称氢化反应,具有很好的活性,且产率较高。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。
Claims (10)
1.噁唑啉型手性N,P配体,其特征在于,所述噁唑啉型手性N,P配体具有式(Ⅰ)结构:
所述R1选自苯基、异丙基、叔丁基;
R2选自异丙基、苯基、苄基;R3为氢。
2.根据权利要求1所述噁唑啉型手性N,P配体,其特征在于,所述R1为异丙基,R2为异丙基。
3.权利要求1~2任一项所述噁唑啉型手性N,P配体的制备方法,其特征在于,包括如下步骤:
S1.制备2-羟甲基噁唑啉类化合物:采用式(Ⅳ)所示手性氨基醇类化合物和乙醇酸溶于溶剂,反应,经后处理得到式(Ⅴ)所示2-羟甲基噁唑啉类化合物;
S2.制备噁唑啉型手性N,P配体:采用步骤S1.制得的式(Ⅴ)所示2-羟甲基噁唑啉类化合物与二取代氯化磷(R1)2PCl在碱作用下,在溶剂中反应,经后处理得到式(Ⅰ)所示噁唑啉型手性N,P配体。
4.根据权利要求3所述制备方法,其特征在于,步骤S1.中,所述后处理为:
当R2为异丙基时,采用减压蒸馏进行提纯,减压蒸馏的温度为111℃;
当R2为苯基、苄基时,将体系冷却至室温,减压过滤、重结晶进行提纯,所述重结晶的溶剂体系为石油醚-乙酸乙酯或正己烷-乙酸乙酯。
5.根据权利要求3所述制备方法,其特征在于,步骤S2.中,当R1为叔丁基时,所述碱为1,1-二氮杂双环[5.4.1]十一碳-7-烯;
当R1为苯基、异丙基时,所述碱为三乙胺。
6.权利要求1~2所述噁唑啉型手性N,P配体在制备噁唑啉型手性N,P配体锰配合物中的应用。
7.噁唑啉型手性N,P配体锰配合物,其特征在于,所述噁唑啉型手性N,P配体锰配合物具有式(Ⅱ)结构:
8.权利要求7所述噁唑啉型手性N,P配体锰配合物的制备方法,其特征在于,包括如下步骤:
将权利要求1~2所述噁唑啉型手性N,P配体和Mn(CO)5Br在惰性氛围下溶于溶剂,室温搅拌反应,经后处理得到噁唑啉型手性N,P配体锰配合物。
9.权利要求7所述噁唑啉型手性N,P配体锰配合物在作为芳酮类化合物的不对称氢化反应催化剂中的应用。
10.一种芳酮类化合物的不对称氢化反应的方法,其特征在于,步骤如下:
将权利要求7所述噁唑啉型手性N,P配体锰配合物、式(Ⅲ)所示芳酮类化合物和硅烷在惰性氛围下置于甲苯中,室温搅拌反应,经后处理得到式(Ⅵ)所示手性醇;
所述R4选自甲基、硝基、甲氧基、苯基、氰基或卤素中的一种;所述R5选自甲基或苯基。
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