CN108187746B - Application of trisilamide rare earth metal complex in catalyzing reaction of aldehyde and allyl boric acid - Google Patents
Application of trisilamide rare earth metal complex in catalyzing reaction of aldehyde and allyl boric acid Download PDFInfo
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Abstract
The invention discloses an application of trisilamine rare earth metal complex in catalyzing aldehyde and allyl boric acid reaction, wherein the allyl alcohol is prepared by taking aldehyde and allyl boric acid as raw materials and the trisilamine rare earth metal complex as a catalyst. The reaction condition is mild, the catalytic activity is improved, the preparation difficulty of the catalyst is reduced, and the post-treatment cost is reduced.
Description
Technical Field
The invention relates to an application technology of a metal organic complex, in particular to an application of a trisilamide rare earth metal complex in catalyzing a boronization reaction of aldehyde and allyl boric acid.
Background
Allyl alcohol is an important intermediate in organic synthesis and is used in many medicineBoth drugs and fine products have a very broad role in the synthesis (Keck, G E.; Covel, J. A.; Schiff. T.; Tao, Y.).Org. Lett. 2002,4, 1189). Among the various processes for preparing allyl alcohols, the allylation of aldehydes is a relatively mature and efficient process. Current studies of the allylation of carbonyl groups have focused mainly on substrate-induced and chiral catalyst-catalyzed asymmetric allylation of aldehydes. Various types of allylsilicon reagents have been developed for substrate induction, but their practical use is severely limited due to the low activity of the silicon reagents. Samir et al also reacted the ligand TADDOL with an allylic metal titanium compound to give a complex, which was then reacted with an aldehyde in an ether solvent at-78 ℃ to give the corresponding allylic alcohol. In the reactions catalyzed by chiral catalysts, chiral phosphoric triamides, catalysts formed by complexing various metal salts (Cd, Ru, Cu, Pd, Ag) with BINAP, chiral oxazoline metal complexes, and the like have been reported. In recent years, the application of chiral phosphoric acid catalyst (R) -TRIP-PA to allylic boronation reaction is reported, and in the previously reported allylation reaction system for catalyzing aldehyde, many harsh conditions such as large using amount of reaction catalyst, low reaction temperature and the like generally exist.
Disclosure of Invention
The invention aims to provide application of a trisilamide rare earth metal complex, namely application of the trisilamide rare earth metal complex as a high-efficiency catalyst for catalyzing aldehyde and allyl boric acid to carry out a boronization reaction, and the trisilamide rare earth metal complex is mild in reaction condition, improves catalytic activity, reduces preparation difficulty of the catalyst and reduces post-treatment cost.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
application of trisilamide rare earth metal complex in catalyzing reaction of aldehyde and allyl boric acid.
The invention also discloses the application of the trisilamide rare earth metal complex in the preparation of allyl alcohol.
The invention also discloses a preparation method of the allyl alcohol, which takes aldehyde and allyl boric acid as raw materials and takes the trisilamine rare earth metal complex as a catalyst to prepare the allyl alcohol.
The molecular formula of the trisilamine rare earth metal complex can be expressed as follows: ln [ N (SiMe) ]3)2]3Ln represents rare earth metal selected from one of lanthanum, neodymium and samarium in lanthanide series; the chemical structural formula of the trisilamide rare earth metal complex is as follows:
the trisilamide rare earth metal complex can catalyze aldehydes to generate allylic boronization reaction with allylic boric acid to prepare allyl alcohol.
In the technical scheme, the method for synthesizing allyl alcohol by catalyzing aldehyde and allyl boric acid to have allylic boronization reaction by taking trisilamide rare earth metal complex as a catalyst comprises the following steps:
adding catalyst Ln [ N (SiMe) into a reaction bottle subjected to dehydration and deoxidation treatment in an anhydrous and oxygen-free environment in an inert gas atmosphere3)2]3Then adding aldehyde, mixing uniformly, adding allylboronic acid by using a syringe, reacting for 1h, exposing to air to terminate the reaction, adding 8mL of HCl solution hydrolysate with the concentration of 1M, stirring for 1h, and purifying by column chromatography (ethyl acetate: n-hexane = 1:10) to obtain the corresponding allyl alcohol.
In the above technical scheme, the aldehyde is selected from one of aromatic aldehyde and aliphatic aldehyde, and the chemical structural general formula of the aromatic aldehyde is
(ii) a Wherein R is one of electron withdrawing group or electron donating group, and can be selected from halogen, methoxy and methyl; the fatty aldehyde is selected from n-heptanal.
In the technical scheme, the using amount of the catalyst can be 0.1-0.5% of the molar weight of aldehyde, the molar ratio of the allyl boronic acid to the aldehyde is 1: 1.2, the reaction temperature is room temperature, and the reaction time is 1 h.
The above technical solution can be expressed as follows:
r comes from the aldehyde which is the reaction raw material.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention firstly adopts a rare earth metal catalytic system to catalyze aldehyde to generate allylic boronization reaction, provides a new scheme for preparing allyl alcohol by adopting carbonyl compound and allylic boric acid to generate allylic boronization reaction, and expands the application of trisilamide rare earth metal complex.
2. The trisilamide rare earth metal complex disclosed by the invention has high catalytic activity (the dosage of the catalyst is only 0.1-0.5% of the molar weight of aldehyde), mild reaction conditions (room temperature), short reaction time (1 h), high reaction efficiency, simple and controllable reaction, simple post-treatment and reduced environmental pollution.
3. The catalyst disclosed by the invention has better universality on aromatic aldehydes and aliphatic aldehydes with different substitution positions and different electronic effects, and provides more choices for obtaining borate compounds with different substituent structures.
Detailed Description
The invention is further described below with reference to examples:
the first embodiment is as follows: la [ N (SiMe)3)2]3Catalytic reaction of benzaldehyde with allylboronic acid
Adding catalyst La [ N (SiMe) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon3)2]30.08mL of 0.01mol/L (0.1 mol percent), then adding 0.081 mL of benzaldehyde (0.8mmol) by a syringe, dissolving the catalyst, mixing uniformly, adding 0.180 mL of allyl boric acid by the syringe, stirring the mixture at room temperature, after reacting for 1h, exposing the mixture to the air to terminate the reaction, adding 8mL of HCl solution hydrolysate with the concentration of 1M, purifying by column chromatography (ethyl acetate: n-hexane = 1:10) to obtain the corresponding allyl alcohol (1-phenyl-3-alkene butanol), wherein the nuclear magnetic yield is 98 percent,the isolation yield was 90%. Nuclear magnetic data of the product:1H NMR (CDCl3，400 MHz): 7.34-7.20 (m, 5H),5.85-5.71 (m, 1H), 5.16-5.10 (m, 2H), 4.72 (dd,J =7.6, 5.6 Hz, 1H), 2.54-2.43 (m, 2H), 2.00 (br s, 1H)。
example two: nd [ N (SiMe)3)2]3Catalytic reaction of benzaldehyde with allylboronic acid
Adding catalyst Nd [ N (SiMe) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon3)2]3Then 0.081 mL of benzaldehyde is added by a syringe, the catalyst is dissolved and mixed evenly, 0.180 mL of allyl boric acid is added by the syringe, the mixture is stirred at room temperature, after 1h of reaction, the reaction is terminated by exposing to the air, 8mL of HCl solution hydrolysate with the concentration of 1M is added, and the corresponding allyl alcohol (1-phenyl-3-alkene butanol) is obtained by purification by column chromatography (ethyl acetate: n-hexane = 1:10), the nuclear magnetic yield is 98 percent, and the separation yield is 90 percent. The nuclear magnetic data of the product are the same as in example one.
Example three: sm [ N (SiMe)3)2]3Catalytic reaction of benzaldehyde with allylboronic acid
Adding catalyst Sm [ N (SiMe) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon3)2]3Then 0.081 mL of benzaldehyde is added by a syringe, the catalyst is dissolved and mixed evenly, 0.180 mL of allyl boric acid is added by the syringe, the mixture is stirred at room temperature, after 1h of reaction, the reaction is terminated by exposing to the air, 8mL of HCl solution hydrolysate with the concentration of 1M is added, and the corresponding allyl alcohol (1-phenyl-3-alkene butanol) is obtained by purification by column chromatography (ethyl acetate: n-hexane = 1:10), wherein the nuclear magnetic yield is 97% and the separation yield is 90%. The nuclear magnetic data of the product are the same as in example one.
Example four: la [ N (SiMe)3)2]3Catalyzing the reaction of p-fluorobenzaldehyde and allylboronic acid
In the reaction bottle which is subjected to dehydration and deoxidation treatment,adding catalyst La [ N (SiMe) under the protection of argon3)2]3Then 0.086 mL p-fluorobenzaldehyde is added by a syringe, the catalyst is dissolved and mixed uniformly, 0.180 mL allyl boric acid is added by the syringe, the mixture is stirred at room temperature, after 1h of reaction, the reaction is terminated by exposing to the air, 8mL of HCl solution hydrolysate with the concentration of 1M is added, and the corresponding allyl alcohol (1- (4-fluorophenyl) -3-alkene butanol) is obtained by purification through column chromatography (ethyl acetate: n-hexane = 1:10), wherein the nuclear magnetic yield is 98% and the separation yield is 91%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400 MHz,): 1.98 (s, 1H), 2.39-2.53 (m, 2H), 4.59-4.73 (m, 1H), 4.96-5.21 (m, 2H), 5.69-5.85 (m, 1H), 7.16-7.35 (m, 4H)。
example five: nd [ N (SiMe)3)2]3Catalyzing the reaction of p-fluorobenzaldehyde and allylboronic acid
Adding catalyst Nd [ N (SiMe) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon3)2]3Then 0.086 mL p-fluorobenzaldehyde is added by a syringe, the catalyst is dissolved and mixed uniformly, 0.180 mL allyl boric acid is added by the syringe, the mixture is stirred at room temperature, after 1h of reaction, the reaction is terminated by exposure to the air, 8mL of HCl solution hydrolysate with the concentration of 1M is added, and the corresponding allyl alcohol (1- (4-fluorophenyl) -3-alkene butanol) is obtained by purification through column chromatography (ethyl acetate: n-hexane = 1:10), wherein the nuclear magnetic yield is 97% and the separation yield is 90%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400 MHz,): 1.98 (s, 1H), 2.39-2.53 (m, 2H), 4.59-4.73 (m, 1H), 4.96-5.21 (m, 2H), 5.69-5.85 (m, 1H), 7.16-7.35 (m, 4H)。
example six: nd [ N (SiMe)3)2]3Catalyzing reaction of p-bromobenzaldehyde and allylboronic acid
Adding catalyst Nd [ N (SiMe) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon3)2]30.40mL, 0.01mol/L (0.5% molar amount), thenThen adding 0.080 mL of p-bromobenzaldehyde by using a syringe, dissolving the catalyst, uniformly mixing, adding 0.180 mL of allylboronic acid by using the syringe, stirring the mixture at room temperature, reacting for 1h, exposing the mixture to the air to terminate the reaction, adding 8mL of a 1M HCl solution hydrolysate, and purifying by using column chromatography (ethyl acetate: n-hexane = 1:10) to obtain the corresponding allyl alcohol (1- (4-bromophenyl) -3-alkene butanol), wherein the nuclear magnetic yield is 96% and the separation yield is 90%. Nuclear magnetic data of the product:1H NMR (CDCl3，400 MHz): 7.36 (d, J = 8.4 Hz,2H), 7.17 (d, J = 8.4 Hz, 2H), 5.81-5.69 (m, 1H), 5.17-5.12 (m, 2H), 4.69(dd, J = 7.6, 4.8 Hz, 1H), 2.50-2.36 (m, 2H), 2.04 (br s, 1H)。
example seven: la [ N (SiMe)3)2]3Catalyzing reaction of o-methyl benzaldehyde and allyl boric acid
Adding catalyst La [ N (SiMe) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon3)2]3Then 0.093 mL of o-methylbenzaldehyde was added by a syringe, the catalyst was dissolved, the mixture was uniformly mixed, 0.180 mL of allylboronic acid was added by a syringe, the mixture was stirred at room temperature for 1 hour, and after the reaction was terminated by exposure to air, 8mL of a 1M HCl solution hydrolysate was added, and the reaction product was purified by column chromatography (ethyl acetate: n-hexane = 1:10) to obtain the corresponding allylic alcohol (1- (2-methylphenyl) -3-enebutanol), with a nuclear magnetic yield of 98% and an isolation yield of 91%. Nuclear magnetic data of the product:1H NMR (CDCl3，400 MHz): 7.45 (d, J = 7.8 Hz,1H), 7.28-7.09 (m, 3H) 5.17-5.10 (m, 2H), 4.95 (dd, J = 8.0, 4.8 Hz, 1H),2.50-2.41 (m, 2H), 2.35 (s, 3H), 1.97 (br s, 1H)。
example eight: nd [ N (SiMe)3)2]3Catalyzing reaction of o-methyl benzaldehyde and allyl boric acid
Adding catalyst Nd [ N (SiMe) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon3)2]30.5% molar amount, and then 0.093 mL of o-methylbenzaldehyde was added by syringeDissolving the catalyst, uniformly mixing, adding 0.180 mL of allylboronic acid by using an injector, stirring the mixture at room temperature, reacting for 1h, exposing the mixture to the air to terminate the reaction, adding 8mL of a 1M HCl solution hydrolysate, and purifying by using column chromatography (ethyl acetate: n-hexane = 1:10) to obtain the corresponding allyl alcohol (1- (2-methylphenyl) -3-alkene butanol), wherein the nuclear magnetic yield is 99% and the separation yield is 91%. Nuclear magnetic data of the product:1H NMR (CDCl3，400 MHz): 7.45 (d, J = 7.8 Hz,1H), 7.28-7.09 (m, 3H) 5.17-5.10 (m, 2H), 4.95 (dd,J= 8.0, 4.8 Hz, 1H),2.50-2.41 (m, 2H), 2.35 (s, 3H), 1.97 (br s, 1H)。
example nine: nd [ N (SiMe)3)2]3Catalytic reaction of p-tolualdehyde with allylboronic acid
Adding catalyst Nd [ N (SiMe) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon3)2]3Then 0.094 mL of p-tolualdehyde was added by syringe, the catalyst was dissolved, mixed well, 0.180 mL of allylboronic acid was added by syringe, the mixture was stirred at room temperature for 1 hour, and after the reaction was terminated by exposure to air, 8mL of a 1M HCl solution hydrolysate was added and purified by column chromatography (ethyl acetate: n-hexane = 1:10) to give the corresponding allylic alcohol (1- (4-methylphenyl) -3-vinylbutanol) with a nuclear magnetic yield of 99% and an isolation yield of 91%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400 MHz): 7.25-7.11 (m, 4H),5.90-5.63 (m, 1H), 5.24-5.09 (m, 2H), 4.71 (dd,J= 6.8, 1H), 2.49 (tt, 6.4Hz, 2H), 2.41 (s, 3H), 2.01 (br s, 1H)。
example ten: nd [ N (SiMe)3)2]3Catalytic reaction of p-methoxybenzaldehyde and allylboronic acid
Adding catalyst Nd [ N (SiMe) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon3)2]30.5 mol/L, then 0.097 mL p-methoxybenzaldehyde was added by syringe, the catalyst was dissolved, mixed well, and then the mixture was injected by syringe0.180 mL of allylboronic acid was added, the mixture was stirred at room temperature, and after 1h of reaction, the reaction was terminated by exposure to air, and 8mL of a 1M HCl solution hydrolysate was added and purified by column chromatography (ethyl acetate: n-hexane = 1:10) to give the corresponding allylic alcohol (1- (4-methoxyphenyl) -3-en-butanol) in 99% nuclear magnetic yield and 91% isolated yield. Nuclear magnetic data of the product:1H NMR (CDCl3，400 MHz): 7.24 (d,J= 8.0,2H), 6.79 (d,J= 8.0, 2H), 5.81-5.70 (m, 1H), 5.15-5.11 (m, 2H), 4.67 (m,1H), 3.76 (s, 3H), 2.47 (m, 2H), 1.97(br s, 1H)。
example eleven: nd [ N (SiMe)3)2]3Catalysis of reaction of n-heptanal with allylboronic acid
Adding catalyst Nd [ N (SiMe) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon3)2]3Then 0.113 mL of n-heptanal is added by a syringe, the catalyst is dissolved and mixed uniformly, 0.180 mL of allyl boronic acid is added by a syringe, the mixture is stirred at room temperature, after 1h of reaction, the reaction is terminated by exposure to the air, 8mL of a 1M HCl solution hydrolysate is added, and the corresponding allyl alcohol (1-decen-4-ol) is obtained by purification by column chromatography (ethyl acetate: n-hexane = 1:10), with a nuclear magnetic yield of 98% and a separation yield of 90%. Nuclear magnetic data of the product:1H NMR (CDCl3，400 MHz): 5.83 (m, 1H), 4.88 (d,J= 6.8, 2H),4.76 (br s, 1H), 3.52 (m, 2H), 2.20 (m, 2H), 1.42 (m, 2H), 1.25 (m, 6H), 0.87(s, 3H)。
the rare earth metal complex is adopted to catalyze the reaction of aldehyde and allyl boric acid, the amount of the catalyst is extremely low (0.1-0.5%), the reaction condition is mild (room temperature), and a foundation is provided for industrial production; in addition, the rare earth metal complex is used for catalyzing the reaction for the first time, and the application range of the rare earth metal organic complex is expanded.
Claims (1)
1. The application of the trisilicamine rare earth metal complex in catalyzing the reaction of aldehyde and allyl boric acid is characterized in that the chemical structural formula of the trisilicamine rare earth metal complex is as follows:
the dosage of the trisilamide rare earth metal complex is 0.1-0.5% of the molar weight of aldehyde; ln is selected from one of lanthanum, neodymium and samarium;
the aldehyde is selected from one of benzaldehyde, p-fluorobenzaldehyde, p-bromobenzaldehyde, o-methylbenzaldehyde, p-methylbenzaldehyde and p-methoxybenzaldehyde.
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