CN113563372B - Alkenyl borate synthesis method - Google Patents

Alkenyl borate synthesis method Download PDF

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CN113563372B
CN113563372B CN202111012403.4A CN202111012403A CN113563372B CN 113563372 B CN113563372 B CN 113563372B CN 202111012403 A CN202111012403 A CN 202111012403A CN 113563372 B CN113563372 B CN 113563372B
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phenylacetylene
alkyne
catalyst
reaction
lithium
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CN113563372A (en
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邵银林
刘继超
施茵茵
胡霆辉
杨薇
巫彩燕
谢瑶瑶
胡方成
王越
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Institute of New Materials and Industrial Technology of Wenzhou University
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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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds

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Abstract

The invention discloses a method for synthesizing alkenyl borate, which comprises the steps of adding alkyne substances, pinacol borane and a lithium amide catalyst into a reaction vessel filled with an organic solvent under the atmosphere of nitrogen, stirring and mixing, reacting at 70-110 ℃ after uniform mixing for 18-28h, and filtering and purifying after the reaction is finished to obtain a product; the lithium amide catalyst is lithium bis (trimethylsilyl) amide; the alkyne substance is any one of phenylacetylene, 4-methyl phenylacetylene and the like; the invention has mild reaction conditions, easy achievement and safety; the invention can directly synthesize the target product without separating intermediate products, and the yield can reach 98 percent at maximum; the catalyst is easy to prepare, and the reactant raw materials are easy to obtain; the invention reduces the discharge of the waste solution, and has the advantages of protecting the environment and guaranteeing the health of operators.

Description

Alkenyl borate synthesis method
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing alkenyl borate.
Background
Organoboron chemistry has been an extremely important part of the chemical field from none to the last. The discovery of the suzuki coupling reaction (Suzuki coupling reaction) enables the organic borate compounds to be effectively applied to the construction of carbon-carbon bonds, not only can be widely touted in the field of organic synthesis, but also can be widely applied in the fields of material chemistry and pharmaceutical chemistry. Therefore, efficient and convenient synthesis of organic borate raw materials is particularly important.
In recent years, the synthesis of organic carbon compounds is an important task because carbon-boron bonds are easily converted into various carbon-carbon and carbon heteroatomic bonds; in particular, transition metal catalysis has become an important synthetic strategy for synthesizing alkenyl borates from alkyne hydroboranyl. In the prior art for preparing alkenyl borate, the prior art is always dependent on Rh, ru, ir, fe and other transition metals, and reports of low-cost and easily available alkali metal catalyzed polysubstituted alkyne hydroboration are few. Literature (org. Chem. Front., 2019, 6, 2949-2953) reports that an n-butyllithium promotes hydroboration, but the reaction conditions are severe and the functional group tolerance is poor. The literature (Angew. Chem. Int. Ed. 2016, 55, 15356-15359) reports the aluminium catalyzed boronation of alkynes but with generally lower yields and cumbersome catalyst preparation, with certain limitations, which also limits alkenyl borates.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a synthesis method of alkenyl borate, which takes lithium amide as a catalyst, has the advantages of easy preparation of the catalyst, easily obtained reactant raw materials, simple reaction process, safety and high yield.
In order to achieve the above purpose, the present invention provides the following technical solutions: the synthesis process of alkenyl borate includes adding alkyne, pinacol borane (HBpin) and lithium amide catalyst into reaction container with organic solvent under nitrogen atmosphere, stirring to mix, reaction at 70-110 deg.c for 18-28 hr, filtering and purifying to obtain alkenyl borate.
As a further improvement of the invention, the lithium amide catalyst is lithium bis (trimethylsilyl) amide (LiN (TMS) 2 ) Abbreviated as LHMDS.
As a further improvement of the invention, the alkyne substance is any one of phenylacetylene, 4-methyl phenylacetylene, 4-ethyl phenylacetylene, 4-tertiary butyl phenylacetylene, 4-phenyl phenylacetylene, 4-fluoro phenylacetylene, terephthalylene, 4-methoxy phenylacetylene, tertiary butyl acetylene and cyclohexenyl acetylene.
As a further improvement of the invention, the molar ratio of the alkyne substance to the pinacol borane added is 1:1.1-1.5.
As a further improvement of the invention, the molar ratio of the alkyne substance to the lithium amide catalyst is 1:0.04-0.10.
As a further improvement of the present invention, the organic solvent is toluene.
The reaction formula of the invention is as follows:
；
the reaction mechanism of the invention:
；
firstly, reacting pinacol borane with lithium silamide to obtain a lithium hydride intermediate, inserting a carbon-carbon triple bond into the lithium hydride intermediate A to obtain an alkenyl lithium intermediate B, and reacting the alkenyl lithium intermediate B with the pinacol borane to obtain products alkenyl boron and the lithium hydride intermediate, so as to complete catalytic cycle.
The inventor of the invention through intensive researches, discovers that the method has high atom economy, high bond forming efficiency and mild reaction conditions, and can catalyze alkyne hydroboration reaction under a lithium silamine catalytic system so as to realize the synthesis of alkenyl borate with diversified structures. The reaction conditions and substrate universality are significantly improved compared with the prior methods, which is difficult to realize by other methods. The organic boron reagent prepared by the method has high quality, high yield, good reaction universality, high economy of reaction atoms and convenient post-treatment; realizes the construction of organoboron compounds by base-catalyzed alkyne hydroboration, and provides an important reference for construction of organoboron reagents.
The invention has the beneficial effects that:
(1) The reaction universality is good, the yield is high, most of the reaction yield is over 90 percent, and the atom economy is high;
(2) The method is an important supplement to alkyne hydroboration, and provides an important thought for constructing compounds containing organic boron;
(3) The reaction conditions are mild and do not require large/cumbersome additives;
(4) The lithium silicate catalyst has simple structure, low price and no metal catalyst.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
（E) -preparation of 4, 5-tetramethyl-2-styryl-1, 3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, raw materials of phenylacetylene (0.5 mmol), pinacol borane (0.6 mmol) and a catalyst LHMDS are added into a reaction vessel(7 mol%) and toluene (0.5 mL) are stirred and mixed, and reacted at 80 ℃ for 24 h after being uniformly mixed, filtered and purified to prepare a product; the product isolation yield was 98%.
1 H NMR (500 MHz, CDCl 3 ):δ7.50–7.48 (m, 2H), 7.40 (d,J= 18.5 Hz, 1H), 7.35–7.26 (m, 3H), 6.17 (d,J= 18.5 Hz, 1H), 1.31 (s, 12H). 13 C NMR (125 MHz, CDCl 3 ):δ149.7, 137.6, 129.0, 128.7, 127.2, 83.5, 24.9.
Example 2
(E) -preparation of 4, 5-tetramethyl-2- (4-methyl styryl) -1,3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw material 4-methyl phenylacetylene into a reaction container0.5 mmol), pinacolborane (0.6 mmol), catalyst LHMDS(7 mol%) and toluene (0.5 mL) are stirred and mixed, and reacted at 80 ℃ for 24 h after being uniformly mixed, filtered and purified to prepare a product; the product isolation yield was 89%.
1 H NMR (500 MHz, CDCl 3 ) δ 7.40 - 7.36 (m, 3H), 7.12 - 7.10 (m, 2H), 6.11 (d,J = 18.5 Hz, 1H), 2.31 (s, 3H), 1.29 (s, 12H). 13 C NMR (125 MHz, CDCl 3 ) δ 149.5, 138.9, 134.8, 129.3, 127.0, 83.2, 24.8, 21.3.
Example 3
(E) -preparation of 2- (4-ethylstyryl) -4, 5-tetramethyl-1, 3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, 4-ethyl phenylacetylene (0.5 mmol), pinacol borane (0.6 mmol) and LHMDS catalyst are added into a reaction vessel(7 mol%) and toluene (0.5 mL) are stirred and mixed, and reacted at 80 ℃ for 24 h after being uniformly mixed, filtered and purified to prepare a product; the product isolation yield was 89%.
1 H NMR (500 MHz, CDCl 3 ) δ 7.41 - 7.37 (m, 3H), 7.15 (d,J = 8.0 Hz, 2H), 6.12 (d,J= 18.5 Hz, 1H) 2.62 (q,J= 8.0 Hz, 2H), 1.32 (s, 12H), 1.21 (t,J= 8.0 Hz, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ 149.6, 145.3, 135.1, 128.1, 127.2, 115.4 (br, C-B), 83.3, 28.8, 24.9, 15.5.
Example 4
(E) -preparation of 2- (4- (tert-butyl) styryl) -4, 5-tetramethyl-1, 3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw material 4-tertiary into a reaction vesselButyl phenylacetylene (0.5 mmol), pinacol borane (0.6 mmol), catalyst LHMDS(7 mol%) and toluene (0.5 mL) are stirred and mixed, and reacted at 80 ℃ for 24 h after being uniformly mixed, filtered and purified to prepare a product; the product isolation yield was 88%.
1 H NMR (500 MHz, CDCl 3 ) δ 7.45 - 7.35 (m, 5H), 6.12 (d,J = 18.5 Hz, 1H), 1.31 (s, 21H). 13 C NMR (125 MHz, CDCl 3 ) δ 152.2, 149.5, 134.9, 126.9, 125.6, 83.4, 34.8, 31.4, 24.9.
Example 5
(E) -2- (2- ([ 1,1' -biphenyl)]-4-yl) vinyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane, having the structural formula:
the preparation method comprises the following steps: under the protection of nitrogen, 4-phenylphenylacetylene (0.5 mmol), pinacol borane (0.6 mmol) and catalyst LHMDS are added into a reaction vessel(7 mol%) and toluene (0.5 mL) are stirred and mixed, and reacted at 80 ℃ for 24 h after being uniformly mixed, filtered and purified to prepare a product; the product isolation yield was 90%.
1 H NMR (500 MHz, CDCl 3 ) δ 7.60 - 7.55 (m, 6H), 7.46 - 7.41 (m, 3H), 7.35 - 7.32 ( m, 1H), 6.21 (d, J = 18.5, 1H), 1.32 (s, 12H). 13 C NMR (125 MHz, CDCl 3 ) δ 149.1, 141.7, 140.6, 136.6, 128.9, 127.6, 127.5, 127.3, 127.0, 83.4, 24.9.
Example 6
（E) -preparation of 2- (4-fluorostyryl) -4, 5-tetramethyl-1, 3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, 4-fluorophenylacetylene (0.5 mmol) and pinacol borane (0.6 mmol) as raw materials are added into a reaction vessel) Catalyst LHMDS(7 mol%) and toluene (0.5 mL) are stirred and mixed, and reacted at 80 ℃ for 24 h after being uniformly mixed, filtered and purified to prepare a product; the product isolation yield was 97%.
1 H NMR (500 MHz, CDCl 3 ):δ7.47–7.44 (m, 2H), 7.35 (d,J= 18.5 Hz, 1H), 7.02 (t,J= 8.0 Hz, 2H), 6.07 (d,J= 18.5 Hz, 1H), 1.31 (s, 12H). 13 C NMR (125 MHz, CDCl 3 ):δ163.3 (d,J= 248.3 Hz), 148.3, 133.9, 128.8 (d,J= 8.3 Hz), 115.7 (d,J= 21.6 Hz), 83.5, 24.9.
Example 7
1, 4-bis (-)E) -preparation of 2- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) vinyl) benzene having the structural formula:
the preparation method comprises the following steps: under the protection of nitrogen, raw materials of terephthalylene (0.5 mmol), pinacol borane (1.2 mmol) and a catalyst LHMDS are added into a reaction vessel(7 mol%) and toluene (0.5 mL) are stirred and mixed, and reacted at 100 ℃ for 24 h, filtered and purified to obtain the product; the product isolation yield was 78%.
1 H NMR (500 MHz, CDCl 3 ) δ 7.45 (s, 4H), 7.36 (d, J = 18.5 Hz, 2H), 6.16 (d, J = 18.5 Hz, 2H), 1.31 (s, 24H); 13 C NMR (125 MHz, CDCl 3 ) δ 148.7, 137.8, 127.2, 119.6（br, C-B）, 83.8, 24.8.
Example 8
（E) -preparation of 2- (4-methoxystyryl) -4, 5-tetramethyl-1, 3, 2-dioxaborane, the structural formula is as follows:
the preparation method comprises the following steps: under the protection of nitrogen, adding raw material 4-methoxy phenylacetylene into a reaction vessel(0.5 mmol), pinacolborane (0.6 mmol), catalyst LHMDS(7 mol%) and toluene (0.5 mL) are stirred and mixed, and reacted at 100 ℃ for 24 h, filtered and purified to obtain the product; the product isolation yield was 98%.
1 H NMR (500 MHz, CDCl 3 ) δ 7.49 – 7.39 (m, 2H), 7.35 (d,J = 18.5 Hz, 1H), 6.92 – 6.80 (m, 2H), 6.01 (d,J= 18.5 Hz, 1H), 3.81 (s, 3H), 1.31 (s, 12H). 13 C NMR (125 MHz, CDCl 3 ) δ 160.3, 149.0, 130.4, 128.4, 113.9, 83.2, 55.3, 24.8.
Example 9
(E) -preparation of 2- (3, 3-dimethylbut-1-en-1-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborane, having the structural formula:
the preparation method comprises the following steps: under the protection of nitrogen, the raw material tert-butyl acetylene (0.5 mmol), pinacol borane (0.6 mmol) and the catalyst LHMDS are added into a reaction vessel(7 mol%) and toluene (0.5 mL) are stirred and mixed, the mixture is reacted at 100 ℃ for 24 h, and the product is obtained after filtration and purification, and the product separation yield is 80%.
1 H NMR (500 MHz, CDCl 3 ) d 6.64 (d,J= 18.5 Hz, 1H), 5.35 (d,J= 18.5Hz, 1H), 1.28 (s, 12H), 1.02 (s, 9H). 13 C NMR (125Mz, CDCl 3 ) d 164.5, 112.6(C-B), 83.1, 35.1, 28.9, 24.9.
Example 10
(E) -preparation of 2- (2- (cyclohex-1-en-1-yl) vinyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane, having the structural formula:
the preparation method comprises the following steps: the raw material cyclohexenylacetylene (0.5 mmol), pinacol borane, was charged to the reaction vessel under nitrogen protection(0.6 mmol), catalyst LHMDS(7 mol%) and toluene (0.5 mL) are stirred and mixed, and reacted at 100 ℃ for 24 h, filtered and purified to obtain the product; the product isolation yield was 80%.
1 H NMR (500 MHz, CDCl3) δ 7.02 (d,J = 18.5 Hz, 1H), 5.96 (t,J = 3.9 Hz, 1H), 5.42 (d,J = 18.5 Hz, 1H), 2.22 – 2.07 (m, 4H), 1.76 – 1.47 (m, 4H), 1.27 (s, 12H). 13 C NMR (125 MHz, CDCl3) δ 153.2, 137.1, 134.3, 83.0, 26.2, 24.8, 23.7, 22.4, 22.3.
The method can directly synthesize the target product without separating intermediate products, and only needs stirring reaction under normal pressure to obtain the target product, wherein the highest yield can reach 98%, thus greatly simplifying process engineering, reducing energy consumption and having the advantage of high yield; in addition, the waste solution is less in the reaction process, and other polluted gases and liquid are not discharged, so that the invention reduces the discharge of the waste solution and has the advantages of protecting the environment and guaranteeing the health of operators; the toxicity of the substances used in the invention is lower, thus ensuring the health of operators; in addition, a series of alkenyl borate substances can be prepared, and the method has strong substrate universality and provides better guarantee for developing the alkenyl borate substances.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.

Claims (4)

1. A method for synthesizing alkenyl borate is characterized in that: adding alkyne substances, pinacol borane and a lithium amide catalyst into a reaction vessel filled with an organic solvent under the nitrogen atmosphere, stirring and mixing, reacting at 70-110 ℃ for 18-28h after uniform mixing, and filtering and purifying after the reaction is finished to obtain alkenyl borate;
the lithium amide catalyst is lithium bis (trimethylsilyl) amide;
the alkyne substance is any one of phenylacetylene, 4-methyl phenylacetylene, 4-ethyl phenylacetylene, 4-tertiary butyl phenylacetylene, 4-phenyl phenylacetylene, 4-fluoro phenylacetylene, terephthalylene, 4-methoxy phenylacetylene, tertiary butyl acetylene and cyclohexenyl acetylene.
2. The method for synthesizing an alkenyl borate according to claim 1, wherein: the molar ratio of the alkyne substance to the pinacol borane is 1:1.1-1.5.
3. The method for synthesizing an alkenyl borate according to claim 1, wherein: the molar ratio of the alkyne substance to the lithium amide catalyst is 1:0.04-0.10.
4. The method for synthesizing an alkenyl borate according to claim 1, wherein: the organic solvent is toluene.
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