CN112538096B - Application of half-sandwich rhodium complex containing ortho-carboranyl benzoxazole structure - Google Patents
Application of half-sandwich rhodium complex containing ortho-carboranyl benzoxazole structure Download PDFInfo
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- 239000010948 rhodium Substances 0.000 title claims abstract description 60
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 43
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 title claims description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims abstract description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006722 reduction reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- ZMSUVHHASUJZNH-UHFFFAOYSA-N 2-bromo-1,3-benzoxazole Chemical compound C1=CC=C2OC(Br)=NC2=C1 ZMSUVHHASUJZNH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- -1 alcohol compound Chemical class 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- ULPMRIXXHGUZFA-UHFFFAOYSA-N (R)-4-Methyl-3-hexanone Natural products CCC(C)C(=O)CC ULPMRIXXHGUZFA-UHFFFAOYSA-N 0.000 claims description 3
- MGTGUEKJBFTQQW-UHFFFAOYSA-N 1-chloropentan-2-one Chemical compound CCCC(=O)CCl MGTGUEKJBFTQQW-UHFFFAOYSA-N 0.000 claims description 3
- ZAMFXGFUMGUHHU-UHFFFAOYSA-N 1-methoxypentan-2-one Chemical compound CCCC(=O)COC ZAMFXGFUMGUHHU-UHFFFAOYSA-N 0.000 claims description 3
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- 239000000047 product Substances 0.000 description 24
- 238000012512 characterization method Methods 0.000 description 13
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 13
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RGPBQGGBWIMGMA-BJMVGYQFSA-N 5-[(e)-[5-(4-bromophenyl)-6-hydroxy-3,6-dihydro-1,3,4-oxadiazin-2-ylidene]methyl]-1h-pyrimidine-2,4-dione Chemical compound OC1O\C(=C\C=2C(NC(=O)NC=2)=O)NN=C1C1=CC=C(Br)C=C1 RGPBQGGBWIMGMA-BJMVGYQFSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 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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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- 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
- C07C29/145—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 with hydrogen or hydrogen-containing gases
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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Abstract
The invention relates to an application of a half-sandwich rhodium complex containing an ortho-position carborane alkyl benzoxazole structure, wherein the structural formula of the rhodium complex is as follows:
wherein, ". is a boron hydrogen bond; the preparation method comprises the following steps: firstly, adding an n-BuLi solution into an ortho carborane solution, and then reacting at room temperature for 30-60 min; adding bromo-benzoxazole, and reacting at room temperature for 6-8 h; then [ Cp RhCl ] is added 2 ] 2 Reacting at room temperature for 3-5h, and performing post-treatment to obtain the rhodium complex; the rhodium complex can be used as a catalyst to catalyze the asymmetric reduction reaction of aliphatic chiral alcohol compounds synthesized from aliphatic ketone. Compared with the prior art, the rhodium complex has the advantages of simple preparation method, stable physicochemical properties, high catalytic activity on the asymmetric reduction reaction of the aliphatic ketone, mild reaction conditions and the like.
Description
Technical Field
The invention belongs to the technical field of synthetic chemistry, and relates to an application of a half-sandwich rhodium complex containing an ortho-position carborane alkyl benzoxazole structure.
Background
Chiral alcohol is a high-tech product with high added value, and is widely applied to the fields of medicines, pesticides and the like as an important organic synthesis intermediate. The traditional chiral alcohol preparation method is obtained by multi-stage resolution of racemic alcohol, and the method has the disadvantages of complicated steps, high reagent consumption, more generated waste liquid and great influence on the environment. In recent years, various methods for producing chiral alcohols have been developed to meet the demand of green chemistry. Among the methods, the preparation method of synthesizing the chiral alcohol compound by using hydrogen as a hydrogen source and using a catalyst to catalyze the asymmetric reduction of the aliphatic ketone has the advantages of high atom economy, no generation of a large amount of waste residues, no pollution to the environment and the like, so that the preparation method is widely concerned by a plurality of researchers. However, the current method has the problems of low catalytic activity, poor yield and poor selectivity, so that the industrial application of the method is limited.
Disclosure of Invention
The invention aims to provide application of a half-sandwich rhodium complex containing an ortho-carborane alkyl benzoxazole structure, which is used for solving the problems of low catalytic activity, poor yield and poor selectivity in the existing chiral alcohol catalytic synthesis method.
The purpose of the invention can be realized by the following technical scheme:
a half-sandwich rhodium complex containing an ortho-carboranyl benzoxazole structure has a structural formula shown as follows:
wherein "·" is a boron hydrogen bond.
A preparation method of a half-sandwich rhodium complex containing an ortho-carborane-based benzoxazole structure comprises the following steps:
1) adding the n-BuLi solution into the ortho-carborane solution, and then reacting at room temperature for 30-60 min;
2) adding bromo-benzoxazole, and reacting at room temperature for 6-8 h;
3) adding [ Cp RhCl 2 ] 2 Reacting at room temperature for 3-5h, and carrying out post-treatment to obtain the half-sandwich rhodium complex.
Further, in the step 1), the n-BuLi solution is an n-hexane solution of n-BuLi, and the vicinal carborane solution is a tetrahydrofuran solution of vicinal carborane.
Further, the step 1) is specifically as follows: at the temperature of between 85 ℃ below zero and 70 ℃ below zero, the n-BuLi solution is dripped into the ortho carborane solution, the stirring is continued for 20 to 40min, then the solution is slowly heated to the room temperature, and the reaction is continued for 30 to 60 min.
Further, the n-BuLi, the ortho-carborane, the bromo-benzoxazole and the [ Cp & RhCl ] are 2 ] 2 The molar ratio of (2.2-3.0) to (1: 1: 0.5).
Further, in step 3), the post-treatment process is: and after the reaction is finished, sequentially carrying out standing filtration, decompression and solvent extraction, and column chromatography separation on the obtained product mixed solution to obtain the half-sandwich rhodium complex.
Furthermore, in the process of column chromatography separation, the eluent is a mixed reagent consisting of petroleum ether and tetrahydrofuran in a volume ratio of (5-10) to 1.
The half-sandwich rhodium complex is used as a catalyst and is used for catalyzing asymmetric reduction reaction of aliphatic chiral alcohol compounds synthesized from aliphatic ketone.
Further, the asymmetric reduction reaction comprises: mixing an ethanol solution of the half-sandwich rhodium complex with aliphatic ketone, reacting in a reducing agent hydrogen atmosphere, and then sequentially concentrating and separating by silica gel column chromatography to obtain the aliphatic chiral alcohol compound;
wherein the molar ratio of the half-sandwich rhodium complex to the aliphatic ketone is 1 (500-1000), the reaction pressure is 0.05-0.15MPa, the reaction temperature is 80-120 ℃, and the reaction time is 60-300 min;
the aliphatic ketone comprises at least one of butanone, 2-pentanone, 3-hexanone, 1-chloro-2-pentanone or 1-methoxy-2-pentanone.
The preparation method is simple and green, the obtained trivalent rhodium complex can efficiently catalyze the asymmetric reduction of the aliphatic ketone to synthesize the chiral alcohol compound, can catalyze a plurality of types of substrates, has good universality, has higher catalytic activity on the substrates with different electronic effects and steric hindrance effects, has high catalytic efficiency and low cost, is easy to separate products, can not generate a large amount of waste residues, has high catalyst stability, and is insensitive to air and water. In addition, the trivalent rhodium complex in the invention and the iridium complex (CN201910375774.5) containing a carboranyl benzimidazole structure developed before the subject group complement each other, and can be respectively used for catalyzing asymmetric reduction reaction of aromatic ketone and aliphatic ketone, so that the target product range of the series of catalytic systems covers chiral aromatic alcohol and chiral aliphatic alcohol, and the trivalent rhodium complex has a wide application prospect in synthesizing chiral alcohol intermediates with different structures.
Compared with the prior art, the invention has the following characteristics:
1) the trivalent rhodium complex containing the ortho-carborane alkyl benzoxazole structure is simple and green in preparation method, has excellent selectivity and high yield, has stable physicochemical properties, and can stably exist in the air for a long time;
2) the trivalent rhodium complex reacts in a normal pressure hydrogen atmosphere, has higher catalytic activity under the mild condition (80-120 ℃), high yield (92-97%) and high enantioselectivity (ee > 99%).
Drawings
FIG. 1 is a thermogravimetric plot of the half-sandwich rhodium complex prepared in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A half-sandwich rhodium complex containing an ortho-carboranyl benzoxazole structure has a structural formula shown as follows:
wherein "·" is a boron hydrogen bond.
The preparation method of the half-sandwich rhodium complex comprises the following steps:
1) at-85 to-70 ℃, dropwise adding n-BuLi in n-hexane solution to o-C 2 B 10 H 12 Stirring for 20-40min, and slowly heating to room temperatureContinuing the reaction at room temperature for 30-60 min;
2) adding bromo-benzoxazole, and reacting at room temperature for 6-8 h;
3) adding [ Cp RhCl 2 ] 2 Reacting at room temperature for 3-5h, standing, filtering, vacuum drying, and separating by column chromatography to obtain red target product, semi-sandwich rhodium complex.
Wherein, n-BuLi, ortho-carborane, bromo-benzoxazole and [ Cp & RhCl 2 ] 2 The molar ratio of (2.2-3.0) to (1: 1: 0.5); in the process of column chromatography separation, the used eluent is a mixed reagent consisting of petroleum ether and tetrahydrofuran in a volume ratio of (5-10) to 1.
The half-sandwich rhodium complex can be used as a catalyst for catalyzing asymmetric reduction reaction of aliphatic chiral alcohol compounds synthesized from aliphatic ketone, and the asymmetric reduction reaction specifically comprises the following processes:
mixing the ethanol solution of the half-sandwich rhodium complex with aliphatic ketone in a molar ratio of 1 (500-1000), reacting at 80-120 ℃ for 60-300min in a hydrogen atmosphere of 0.05-0.15MPa, and then sequentially concentrating and separating by silica gel column chromatography to obtain the aliphatic chiral alcohol compound;
the following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1:
the embodiment is used for synthesizing a half-sandwich rhodium complex [ Rh ] containing an ortho-carborane benzoxazole structure, and the specific preparation method comprises the following steps:
I) a solution of n-BuLi (1.6M) in n-hexane (1.00mL,1.6mmol of n-BuLi) was slowly added dropwise to the o-C containing orthocarborane at-78 deg.C 2 B 10 H 10 (92.0mg,0.64mmol) in tetrahydrofuran and stirring at this temperature for 30 min;
II) slowly heating the product solution obtained in the step I) to room temperature, continuously stirring and reacting for 1h, then adding bromobenzoxazole (126.7mg,0.64mmol), and reacting for 6h at room temperature;
III) reacting a binuclear rhodium compound [ Cp + RhCl 2 ] 2 (256.0mg,0.32mmol) was added to the product solution obtained in step II) and the reaction was stirred for 3 h; after the reaction is finished, sequentially standing, filtering, decompressing and drying the solvent to obtain a crude product, and performing column chromatography separation (petroleum ether/ethyl acetate is 6:1) to obtain a red target product rhodium (III) complex [ Rh (III) ]](245.6mg, 72% yield).
The product characterization results were as follows:
1 H NMR(400MHz,CDCl 3 ,25℃):δ＝7.80(d,J＝6.0Hz,1H),7.71(t,J＝6.0Hz,1H),7.65(d,J＝6.5Hz,1H),7.45(t,J＝6.0Hz,1H),1.67(s,15H,Cp*).
theoretical value of elemental analysis C 19 B 10 H 29 ClRhNO: c42.74, H5.47, N2.62; experimental values: c42.66, H5.50, N2.61.
The characterization results show that the semi-sandwich rhodium complex [ Rh ] containing the ortho-carborane alkyl benzoxazole structure is successfully synthesized in the example.
In addition, this example also performed the evaluation of thermal stability on the rhodium (III) complex [ Rh ], which specifically includes the following steps: 1) heating and refluxing a compound Rh in a toluene solution for three hours, cooling the reaction, draining the solvent, and performing nuclear magnetic characterization on the obtained solid to find that each nuclear magnetic signal is unchanged;
2) 4.5mg of Rh compound was weighed out for thermogravimetric experiments, and the thermogravimetric curve is shown in FIG. 1, which shows that the compound is stable at a high temperature of 300 ℃.
The above test results show that the rhodium (III) complex [ Rh ] synthesized in this example has better thermal stability.
Example 2:
in this example, rhodium (III) complex [ Rh ] in example 1 is used as a catalyst to catalyze an asymmetric reduction reaction of aliphatic ketone, and the specific process is as follows:
by reacting rhodium (III) complexes [ Rh]Adding (0.01mmol,5.3mg) ethanol solution into butanone solution (10mmol,0.72g), introducing hydrogen as a reducing agent under normal pressure, and reacting at 80 deg.C for 120 min; after the reaction is finished, sequentially concentrating, separating by silica gel column chromatography, and drying the product mixed solution to constant weight to obtain the target product chiral alcohol compound C 4 H 10 O (yield 94%), ee>99％。
The product characterization results were as follows:
theoretical value of elemental analysis: c64.82, H13.60; experimental values: c64.89, H13.62, the characterization results show that the example successfully synthesizes the chiral alcohol compound C 4 H 10 O。
Example 3:
in this example, rhodium (III) complex [ Rh ] in example 1 is used as a catalyst to catalyze an asymmetric reduction reaction of aliphatic ketone, and the specific process is as follows:
by reacting rhodium (III) complexes [ Rh]Adding (0.01mmol,5.3mg) ethanol solution into 2-pentanone solution (10mmol,0.86g), introducing hydrogen as a reducing agent under normal pressure, and reacting at 80 deg.C for 60 min; after the reaction is finished, sequentially concentrating, separating by silica gel column chromatography and drying the product mixed solution to constant weight to obtain a target product chiral alcohol compound C 5 H 12 O (92% yield), ee>99％。
The product characterization results were as follows:
theoretical value of elemental analysis: c68.13, H13.72; experimental values: c68.10, H13.81, and the characterization results show that the chiral alcohol compound C is successfully synthesized in the example 5 H 12 O。
Example 4:
in this example, rhodium (III) complex [ Rh ] in example 1 is used as a catalyst to catalyze an asymmetric reduction reaction of aliphatic ketone, and the specific process is as follows:
by reacting rhodium (III) complexes [ Rh]Adding (0.02mmol,10.6mg) ethanol solution into 3-hexanone solution (10mmol,1.00g), introducing hydrogen as a reducing agent under normal pressure to react, controlling the reaction temperature at 120 ℃ and the reaction time at 200 min; after the reaction is finished, sequentially concentrating, separating by silica gel column chromatography, and drying the product mixed solution to constant weight to obtain the target product chiral alcohol compound C 6 H 14 O (97% yield), ee>99％。
The product characterization results were as follows:
theoretical value of elemental analysis: c70.53, H13.81; experimental values: c70.60, H13.77, and the characterization results show that the chiral alcohol compound C is successfully synthesized in the example 6 H 14 O。
Example 5:
in this example, rhodium (III) complex [ Rh ] in example 1 is used as a catalyst to catalyze an asymmetric reduction reaction of aliphatic ketone, and the specific process is as follows:
by reacting rhodium (III) complexes [ Rh]Adding (0.01mmol,5.3mg) ethanol solution into 1-chloro-2-pentanone solution (10mmol,1.20g), introducing hydrogen as a reducing agent under normal pressure, and reacting at 90 deg.C for 150 min; after the reaction is finished, sequentially concentrating, separating by silica gel column chromatography and drying the product mixed solution to constant weight to obtain a target product chiral alcohol compound C 5 H 11 ClO (93% yield), ee>99％。
The product characterization results were as follows:
theoretical value of elemental analysis: c48.99, H9.04; experimental values: c48.90, H9.07, characterization results show that this example becomesSuccessfully synthesized chiral alcohol compound C 5 H 11 ClO。
Example 6:
in this example, rhodium (III) complex [ Rh ] in example 1 is used as a catalyst to catalyze an asymmetric reduction reaction of aliphatic ketone, and the specific process is as follows:
by reacting rhodium (III) complexes [ Rh](0.01mmol,5.3mg) of ethanol solution is added into 1-methoxy-2-pentanone solution (10mmol, 1.16 g), and hydrogen is introduced as a reducing agent to react under normal pressure, the reaction temperature is controlled at 90 ℃, and the reaction time is 120 min; after the reaction is finished, sequentially concentrating, separating by silica gel column chromatography and drying the product mixed solution to constant weight to obtain a target product chiral alcohol compound C 6 H 14 O 2 (yield 92%), ee>99％。
The product characterization results were as follows:
theoretical value of elemental analysis: c60.98, H11.94; experimental values: c60.99, H11.90, and the characterization results show that the chiral alcohol compound C is successfully synthesized in the example 6 H 14 O 2 。
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. The application of the semi-sandwich rhodium complex containing the ortho-carborane-based benzoxazole structure is characterized in that the structural formula of the rhodium complex is as follows:
wherein "·" is a boron hydrogen bond;
the half-sandwich rhodium complex is used as a catalyst for catalyzing asymmetric reduction reaction of aliphatic chiral alcohol compounds synthesized from aliphatic ketone, and comprises the following components: mixing the half-sandwich rhodium complex solution with aliphatic ketone, reacting in a hydrogen atmosphere, and then carrying out post-treatment to obtain the aliphatic chiral alcohol compound;
wherein the molar ratio of the half-sandwich rhodium complex to the aliphatic ketone is 1 (500-1000), the reaction pressure is 0.05-0.15MPa, the reaction temperature is 80-120 ℃, and the reaction time is 60-300 min;
the aliphatic ketone is one of butanone, 2-pentanone, 3-hexanone, 1-chloro-2-pentanone or 1-methoxy-2-pentanone.
2. The use of a half-sandwich rhodium complex containing an ortho-carboranyl benzoxazole structure according to claim 1, wherein the rhodium complex is prepared by a method comprising the steps of:
1) adding the n-BuLi solution into the ortho-carborane solution, and then reacting at room temperature for 30-60 min;
2) adding bromo-benzoxazole, and reacting at room temperature for 6-8 h;
3) adding [ Cp + RhCl ] 2 ] 2 Reacting at room temperature for 3-5h, and carrying out post-treatment to obtain the half-sandwich rhodium complex.
3. The use of a half-sandwich rhodium complex containing a vicinal carborane benzoxazole structure according to claim 2, wherein in step 1), the n-BuLi solution is n-hexane solution of n-BuLi, and the vicinal carborane solution is tetrahydrofuran solution of vicinal carborane.
4. The use of a half-sandwich rhodium complex containing an ortho-carborane-based benzoxazole structure according to claim 2, wherein step 1) is specifically: at the temperature of between 85 ℃ below zero and 70 ℃ below zero, the n-BuLi solution is dripped into the ortho carborane solution, the stirring is continued for 20 to 40min, then the solution is slowly heated to the room temperature, and the reaction is continued for 30 to 60 min.
5. Use of a half-sandwich rhodium complex containing an ortho-carboranyl benzoxazole structure according to claim 2, wherein the n-BuLi, ortho-carborane, bromo benzoxazole and [ Cp × RhCl ] are present 2 ] 2 The molar ratio of (2.2-3.0) to (1: 1: 0.5).
6. The use of a half-sandwich rhodium complex containing an ortho-carboranyl benzoxazole structure according to claim 2, wherein in step 3), the post-treatment process is: and after the reaction is finished, sequentially carrying out standing filtration, decompression and solvent extraction, and column chromatography separation on the obtained product mixed solution to obtain the half-sandwich rhodium complex.
7. The application of the half-sandwich rhodium complex containing the ortho-carborane-based benzoxazole structure according to claim 6, wherein in the column chromatography separation process, the eluent is a mixed reagent of petroleum ether and tetrahydrofuran in a volume ratio of (5-10): 1.
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