CN114315874B - Method for preparing tetra-substituted alkenyl borate derivative - Google Patents
Method for preparing tetra-substituted alkenyl borate derivative Download PDFInfo
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- CN114315874B CN114315874B CN202011030039.XA CN202011030039A CN114315874B CN 114315874 B CN114315874 B CN 114315874B CN 202011030039 A CN202011030039 A CN 202011030039A CN 114315874 B CN114315874 B CN 114315874B
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Abstract
The present invention relates to a process for preparing tetra-substituted alkenyl borate derivatives. Specifically, tetrasubstituted alkenyl borate compounds are prepared from tetralin, pinacol borate and acyl chloride by a one-pot method under the catalysis of copper. The tetra-substituted alkenyl borate compound is obtained by starting from simple and easily available raw materials and performing a copper-catalyzed carboboronation reaction of the tetraene.
Description
Technical Field
The invention relates to a method for synthesizing tetra-substituted alkenyl borate compounds.
Background
Organic carbon compounds play an indispensable role in synthetic chemistry because the C-B bond is easily subjected to various useful transformations, for example, transition metal catalyzed cross-coupling reactions. Of all classes of organoboron compounds, of particular interest are tetra-substituted alkenyl borates, which can be used as universal precursors for the preparation of tetra-substituted olefins that are widely present in biologically active molecules. Thus, in the last decade, the preparation of tetra-substituted alkenyl borates has made remarkable progress. However, most known processes are limited to the use of alkynes as starting materials. Under such circumstances, there remains a great need to develop other effective structural units for synthesizing tetra-substituted alkenyl borate compounds.
In summary, a simple and readily available method for preparing tetra-substituted alkenyl borate derivatives by reacting an acid chloride, a bisboronic acid pinacol ester and a bisene is described herein.
Disclosure of Invention
The invention aims to provide a method for synthesizing tetra-substituted alkenyl borate derivatives.
The specific operation steps are as follows (reaction equation 1):
the operation of catalyst pretreatment is carried out in a glove box, the reaction is carried out in a reactor, firstly, alkali, the bisboronic acid pinacol ester 2, the catalyst, the ligand and the solvent are added, the mixture is stirred for 5 to 30 minutes, preferably 15 minutes in advance, then, the bisene 1 and the acyl chloride are added, and the mixture is reacted for 1 to 24 hours, preferably 12 hours at 70 to 160 ℃, preferably 90 ℃; after the reaction, the tetra-substituted alkenyl borate derivative 4 is separated.
The molar ratio of the diene 1 to the pinacol ester 2 of the bisboric acid is 1:1-3, preferably 1:1.1.
The mol dosage ratio of the diene 1 to the acyl chloride 3 is 1:1-5, and the preferable ratio is 1:2.0.
The catalyst is one or more than two of cuprous chloride, cuprous bromide, cuprous iodide and cupric acetate, preferably cuprous iodide; the catalyst is used in an amount of 0.1mol% to 50mol%, preferably 10mol%, based on the amount of anhydride 1.
The ligand is one or more than two of 1, 3-bis (2, 4, 6-trimethylphenyl) imidazole chloride, 1, 3-bis (2, 6-diisopropylphenyl) imidazole hydrochloride and 1, 3-bis (tert-butylimidazole) chloride; the amount of ligand is 0.1mol% to 50mol%, preferably 11mol%, of the amount of diene 1.
The alkali is one or more of lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide and potassium ethoxide, preferably lithium tert-butoxide; the amount of base is 0.1mol% to 300mol%, preferably 200mol%, of the amount of diene 1.
The solvent is one or more of toluene, tetrahydrofuran, 1, 4-dioxane and cyclohexane, preferably toluene; the solvent is used in an amount of 5 to 50 ml, preferably 10 ml, of solvent per millimole of the diene 1.
The invention has the following advantages:
firstly, the raw materials needed for the reaction are simple to synthesize, and in addition, the bisboronic acid pinacol ester and the acyl chloride are simple and commercially available and belong to bulk chemicals, and the price is low.
Secondly, the reaction realizes the synthesis of tetra-substituted alkenyl borate by the carbonyl boration reaction of copper catalysis diene for the first time, and is different from the synthesis of tetra-substituted alkenyl borate by the prior alkyne precursor.
In addition, the tetra-substituted alkenyl borate compound synthesized by the method has C-B bond, so that the coupling reaction catalyzed by transition metal can be conveniently realized, various derivative compounds can be obtained, and the method can be applied to development and research of natural products, functional materials and fine chemicals.
Detailed Description
For a better understanding of the present invention, it is illustrated by the following examples. The starting materials and results for examples 1-10 are shown in Table 1.
TABLE 1 reaction results of various substituted dienes, dipinacols and acid chlorides
Example 1
In a glove box, the reaction was carried out in a reaction tube, first, alkali (0.4 mmol,2.0 eq.) of lithium t-butoxide, 2 (0.22 mmol,1.1 eq.) of pinacolone ester, cuprous iodide (0.02 mmol,10 mol%), 1, 3-bis (2, 4, 6-trimethylphenyl) imidazole chloride (0.022 mmol,11 mol%) and toluene solvent (2.0 mL) were added, stirred for 5 to 30 minutes (15 minutes in this case), then, allene 1a (0.2 mmol,1.0 eq.) and acyl chloride 3a (0.4 mmol,2.0 eq.) were added, a sealing plug at the opening of the reaction tube was screwed (closed reaction vessel), and the reaction tube was taken out of the glove box to react at 90 ℃ for 12 hours; after the reaction is finished, the tetra-substituted vinyl borate 4aa yield is 58% through column chromatography separation, and the compound is subjected to nuclear magnetism (hydrogen spectrum and carbon spectrum) and high-resolution mass spectrum identification structure.
The detection data are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.63(dd,J＝8.4,1.4Hz,2H),7.53-7.47(m,1H),7.38-7.32(m,3H),7.28-7.23(m,2H),7.10(dd,J＝7.5,2.0Hz,2H),2.04(s,3H),1.36(s,12H)； 13 C NMR(100MHz,CDCl 3 )δ198.0,142.9,135.4,134.2,133.2,131.6,129.6,128.6,128.1,127.7,81.7,25.2,17.8； 11 B NMR(128MHz,CDCl 3 )δ18.7,HRMS calculated for C 22 H 26 BO 3 [M+H] + 349.1970,found349.1979.
by further derivatizing 4aa to give product 5, we can determine that 5 is in cis configuration by single crystal structure of 5, and thus determine that 4aa is in E-type structure. The derivatization reaction is specifically performed as follows:
in a glove box, 4aa (0.2 mmol), 4-CN-PhBr (0.26 mmol,1.3 eq), pd (OAc) were added to the reaction tube 2 (0.02 mmol,10 mol%) 1,1' -bis (di-tert-butylphosphine) ferrocene (0.022 mmol,11 mol%), K 3 PO 4 (0.4mmol,2.0eq.)，H 2 O (25. Mu.L, 7.0 eq.) and toluene (2.0 mL) were added and the tap was screwed. The reaction tube was taken out of the glove box and reacted at 90℃for 12 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the tetra-substituted olefin compound 5 was isolated by column chromatography (yield: 70%). The compound is subjected to nuclear magnetism (hydrogen spectrum and carbon spectrum), high-resolution mass spectrum and monocrystal result identification structure. The detection data are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.78(d,J＝7.4Hz,2H),7.44-7.25(m,12H),2.21(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ197.6,146.8,140.8,137.7,136.7,136.6,133.1,131.9,129.4,129.0,128.7,128.6,128.3,127.9,118.5,111.1,21.3,HRMS calculated for C 23 H 18 NO[M+H] + 324.1383,found 324.1390.
example 2:
the procedure and conditions were the same as in example 1, except that the solvent was cyclohexane, the yield of product 4ba was 61% and the structure was identified by nuclear magnetism (hydrogen and carbon) and high resolution mass spectrometry, except for the differences described in table 1.
Example 3:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were followed, the base was sodium t-butoxide, the yield of product 4ca was 60%, and the structure was identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry.
Example 4:
the procedure and conditions were the same as in example 1, except that the difference from example 1 was that the amount of cuprous iodide used in the catalyst was 5mol% of that in the case of the biuret 1d, the amount of the ligand 1, 3-bis (2, 4, 6-trimethylphenyl) imidazole chloride was 6mol% of that in the case of the biuret 1, the yield of the product 4da was 40%, and the compound was subjected to nuclear magnetism (hydrogen spectrum and carbon spectrum), high-resolution mass spectrometry to identify the structure.
Example 5:
the procedure and conditions were the same as in example 1, except that the difference from example 1 was that the amount of cuprous iodide used in the catalyst was 20mol% of that in the case of the biuret 1a, the amount of the ligand 1, 3-bis (2, 4, 6-trimethylphenyl) imidazole chloride was 22mol% of that in the case of the biuret 1, the yield of the product 4ab was 61%, and the compound was subjected to nuclear magnetism (hydrogen spectrum and carbon spectrum), high-resolution mass spectrometry to identify the structure.
Example 6:
the procedure and conditions were the same as in example 1, except that, in addition to the differences described in Table 1, B 2 pin 2 The dosage of the catalyst is 1.5 equivalent of that of the diene 1a, the yield of the product 4ac is 51%, and the structure of the compound is identified by nuclear magnetism (hydrogen spectrum and carbon spectrum) and high-resolution mass spectrum.
Example 7:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were followed, the acid chloride was used in an amount of 1.5 equivalents to the amount of the diene 1a, the yield of the product 4ad was 57%, and the structure was identified by nuclear magnetism (hydrogen spectrum and carbon spectrum) and high resolution mass spectrometry.
Example 8:
the procedure and conditions were the same as in example 1, except that the reaction temperature was 70℃and the yield of product 4ae was 56% as compared with example 1, and the structure was identified by nuclear magnetism (hydrogen spectrum and carbon spectrum) and high resolution mass spectrum of the compound, except for the differences described in Table 1.
Claims (7)
1. A process for preparing a tetra-substituted alkenyl borate compound characterized by:
the tetrasubstituted alkenyl borate compound 4 is prepared from the raw materials of the diene 1, the bisboronic acid pinacol ester 2 and the acyl chloride 3 shown in the following formula:
wherein R is 1 Is hydrogen, methyl, methoxy, tert-butyl, phenyl, fluoro, chloro, bromo or naphthyl, R 1 The number of (2) is 1;
R 2 is one or two of hydrogen, methyl, methoxy, fluorine, chlorine, bromine, thienyl or naphthyl, R 2 The number of (2) is 1-2;
the specific operation steps are as follows:
1) Carrying out the operation in a glove box, carrying out the reaction in a reaction tube, adding alkali, bisboronic acid pinacol ester 2, copper catalyst, ligand and solvent, stirring for 5-30 minutes in advance, then sequentially and slowly adding bisene 1 and acyl chloride 3, covering the reaction tube with a cover, screwing, and taking out the reaction tube from the glove box;
2) The reaction tube is reacted for 0.5 to 24 hours at the temperature of 80 to 100 ℃; after the reaction is finished, separating to obtain a tetra-substituted alkenyl borate compound 4;
the copper catalyst is one or more than two of cuprous chloride, cuprous bromide, cuprous iodide and cupric acetate; the ligand is one or more than two of 1, 3-bis (2, 4, 6-trimethylphenyl) imidazole chloride, 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride and 1, 3-bis (tert-butylimidazole) chloride.
2. A method according to claim 1, characterized in that:
the molar dosage ratio of the diene 1 to the bisboronic acid pinacol ester 2 is 1:1-3.
3. A method according to claim 1, characterized in that:
the molar usage ratio of the diene 1 to the acyl chloride 3 is 1:1-5.
4. A method according to claim 1, characterized in that:
the copper catalyst is used in an amount of 0.1mol% to 50mol% based on the amount of the diene 1.
5. A method according to claim 1, characterized in that:
the ligand amount is 0.1mol% to 50mol% of the diene 1 amount.
6. A method according to claim 1, characterized in that:
the alkali is one or more of lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide and potassium ethoxide; the amount of the alkali is 0.1mol% to 300mol% of the amount of the diene 1.
7. A method according to claim 1, characterized in that:
the solvent is one or more of toluene, tetrahydrofuran, 1, 4-dioxane and cyclohexane; the solvent is used in an amount of 5-50 ml per millimole of the diene 1.
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Non-Patent Citations (1)
| Title |
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| Arnaud Boreux等."Acyl Fluorides as Efficient Electrophiles for the Copper-Catalyzed Boroacylation of Allenes".《ACS Catal.》.2017,第7卷第8200-8204页. * |
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