WO2004076467A1 - Preparation d'esters diboroniques - Google Patents

Preparation d'esters diboroniques Download PDF

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Publication number
WO2004076467A1
WO2004076467A1 PCT/AU2004/000255 AU2004000255W WO2004076467A1 WO 2004076467 A1 WO2004076467 A1 WO 2004076467A1 AU 2004000255 W AU2004000255 W AU 2004000255W WO 2004076467 A1 WO2004076467 A1 WO 2004076467A1
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diboron
optionally substituted
tetrakis
process according
alcohol
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PCT/AU2004/000255
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English (en)
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Sebastian Mario Marcuccio
Cornelis Matthijs MOORHOFF
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Boron Molecular Pty Ltd
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Publication of WO2004076467A1 publication Critical patent/WO2004076467A1/fr

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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
    • C07F5/022—Boron compounds without C-boron linkages
    • 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
    • C07F5/04—Esters of boric acids

Definitions

  • the invention relates to boronic compounds, in particular to a process for the preparation of diboronic acid and its esters.
  • Diboronic acid and its esters are useful in the preparation of organoboronic acids and esters, which are themselves useful in processes for covalently linking organic compounds.
  • Substituted bi- and tri-aryl compounds are of great interest to the pharmaceutical and agrochemical industries. A great number of these compounds have been found to possess pharmaceutical activity, while others have been found to be useful herbicides.
  • aryl boronic esters which can be readily hydrolysed to the corresponding aryl boronic acid.
  • a great many aryl and alkene boronic acids and esters are most conveniently prepared from the corresponding tetrahydroxydiboron and its ester.
  • Miyaura Ishiyama, T et al. 3. Org. Chem., 1995, 60, 7508 has reported that the diboron ester, bis(pinacolato)diboron, reacts readily with aryl halides in the presence of palladium catalysts to produce arylboronic esters which are then readily converted to arylboronic acids.
  • diboronic esters are important intermediates in the preparation of diboronic compounds for Suzuki coupling with alkene or aryl halides.
  • Many useful reactions involving diboronic esters and organoboronic ester, including aryl and alkenyl boronic esters have been disclosed by Marcuccio et al in the following patent applications by Commonwealth Scientific and Industrial Research Organisation: WO 98/45265, WO 98/58935, WO 99/33845, WO 00/21966 and WO 01/29051.
  • Diboronic esters can be used directly in Suzuki methodology without converting them to their corresponding diboronic acid. In some applications the esters are actually favoured over the analogous acids. For example unlike many parent organoboronic acids the corresponding pinacol esters are discrete molecules which are more easily characterised and may often be purified by chromatography. Furthermore these pinacol esters are generally more soluble in organic solvents. In some instances the pinacol esters can be used as protecting groups to eliminate unwanted side reactions. Also, the use of diboronic esters has been recommended for Suzuki coupling (reaction) in cases where the organoboronic acids are sensitive to hydrolytic deborination.
  • Diboronic esters are generally made following the method of Brotherton et al. [R.J.
  • B(NMe 2 ) 3 obtained by reaction of BC1 3 with NHMe 2 , is converted to BrB(NMe 2 ) 2 by reaction with a stoichiometric amount of BBr 3 .
  • Reduction in refiuxing toluene with sodium metal gives the diboron compound [B(NMe 2 ) 2 ] 2 which, after purification by distillation, can be reacted with the alcohol (for example, pinacol or neopentanediol) in the presence of a stoichiometric amount (four equivalents) of HC1 to give the desired ester product.
  • the alcohol for example, pinacol or neopentanediol
  • the reaction requires the use of anhydrous HC1 which requires the use of specialized equipment that is anti-corrosive in nature. This is especially important for moisture sensitive esters, like the diboronic neopentyl glycolato ester which is susceptible to moisture and prone to lose neopentylglycol.
  • moisture sensitive esters like the diboronic neopentyl glycolato ester which is susceptible to moisture and prone to lose neopentylglycol.
  • excess HC1 may attack the acid sensitive moiety. For instance in the Miyaura et al example mentioned previously, excessive acid may attack the pinacol ester resulting in pinacol-pinacolone rearrangement.
  • the present invention attempts to overcome or eliminate these problems by providing a process for the preparation of diboronic esters which does not require the use of HC1 and does not produce a salt byproduct.
  • diboronic acid tetrahydroxydiboron
  • esters of diboronic acid can be conveniently and efficiently prepared by simply reacting a tetrakis(dialkylamino)diboron with a suitable alcohol under conditions which liberate an alkylamine without using HC1.
  • the present invention provides a process for the preparation of an ester of diboronic acid comprising reacting a tetrakis(dialkylamino)diboron with an alcohol to form said ester and a volatile dialkylamine, wherein the volatile dialkylamine is liberated from the reaction mixture in gaseous form.
  • This process allows for the preparation of diboronic acid esters without using HC1, and without producing significant salt products.
  • the process can also be performed in such a way that liberated amine can be trapped and recycled.
  • the preferred tetrakis(dialkylamino)diboron compounds suitable for use in accordance with the present invention may be represented by formula (I);
  • R and R each independently represent C ⁇ -C 2 alkyl groups.
  • each R and R is identical and is selected from methyl, ethyl, and propyl or R and R together are joined to form a 5 or 6 membered ring system for example a piperidine, or pyrrolidine.
  • the reaction is driven by the concomitant production of the ammonium hydrochloride salt.
  • the present process does not form a similar salt product. Instead, the process of the present invention is thought to be driven by the liberation of a volatile amine from the reaction mixture.
  • the preferred compounds of formula I bear R and R substituents which are small enough to produce volatile amines of the formula HNR'R".
  • the alcohol may be any organic alcohol which is capable of reacting with a tetrakis(dialkylamino)diboron to form an ester of diboronic acid.
  • the alcohol is a compound of formula (Ila):
  • Q is selected from optionally substituted C ⁇ -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted C 2 -C 6 alkynyl, optionally substituted aryl group, or optionally substituted aliphatic ring.
  • the alcohol is a diol of formula (II):
  • n is 2 or 3 and each R is independently selected from hydrogen, optionally substituted C ⁇ -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted C 2 -C 6 alkynyl, optionally substituted Ci-C ⁇ alkoxycarbonyl, optionally substituted C alkoxy, and optionally substituted aryloxy or any two R groups together with the carbon atoms(s) to which they are attached represent an optionally substituted C 5 -C 8 cycloalkyl or C 5 - C 8 cycloalkenyl group.
  • each R is selected from H and methyl.
  • R is not aryl.
  • Preferred diols include pinacol, neopentylglycol, hexyleneglycol and (+)-pinanediol.
  • diols of formula (I) which bear chiral substituents.
  • examples of chiral diols for use in the present invention include (-) or (+)-pinanediol or (D) or (L)-tartrate esters.
  • alkyl used either alone or in compound words such as “alkenyloxy alkyl”, “alkylthio”, “alkylamino” and “dialkylamino” denotes straight chain or branched alkyl, preferably C 1-6 alkyl.
  • straight chain and branched alkyl examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, sec-amyl, 1,2-dimethylpropyl, 1,1 -dimethyl -propyl, hexyl, 4-methylpentyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3- dimethylbutyl, 1 ,2-dimethylbutyl, 1,3-dimethylbutyl, 1 ,2,2,-trimethylpropyl, and 1,1,2- trimethylpropyl .
  • cycloalkyl denotes cyclic alkyl groups, preferably C 5 . 8 cycloalkyl.
  • examples of cycloalkyl include mono- or polycyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
  • alkenyl denotes groups formed from straight chain, or branched alkenes including ethylenically unsaturated alkyl or groups as previously defined, preferably C 2-6 alkenyl.
  • alkenyl include vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3- methyl-2-butenyl, 1-pentenyl, 1-hexenyl, and 3-hexenyl.
  • cycloalkenyl denotes cyclic alkene groups, preferably C 5-8 cycloalkenyl.
  • Examples of cycloalkenyl include cyclopentenyl, methyl cyclopentenyl, cyclohexenyl, cyclooctenyl, 1,3-cyclopentadienyl, 1,3-cyclohexadienyl, and 1,4-cyclohexadienyl.
  • aryl is used herein in the broadest sense to refer to any aromatic ring or ring system, preferably having 3 to 20 carbon atoms.
  • the ring or ring system may contain one or more heteroatoms selected from N, S, and O.
  • the aromatic rings may be carbocyclic, heterocyclic or pseudo aromatic, and may be mono or polycyclic ring systems.
  • suitable rings include but are not limited to benzene, biphenyl, naphthalene, tetrahydronaphthalene, 1-benzylnaphthalene, pyridine, 4-phenylpyridine, 3-phenylpyridine, thiophene, benzothiophene, naphthothiophene, furan, pyrene, isobenzofuram, chromene, pyrrole, imidazole, pyrazole, pyrazine, pyrimidine, pyridazine, indole, indolizine, isoindole, purine, quinoline, isoquinoline, isothiazole, isooxazole, phenoxazine and the like, each of which may be optionally substituted.
  • pseudoaromatic refers to a ring system which is not strictly aromatic, but which is stabilized by means of delocalization of ⁇ electrons and behaves in a similar manner to aromatic rings.
  • pseudoaromatic rings include but are not limited to furan, thiophene, pyrrole and the like.
  • the aryl group is an optionally substituted 5 or 6 membered aromatic ring.
  • aliphatic ring or ring system refers to a non-aromatic carbocyclic or heterocyclic ring or ring system, preferably having from 3 to 20 carbon atoms.
  • the ring or ring system may have one or more double or triple bonds.
  • suitable aliphatic rings include but are not limited to cyclobutane, cyclopentadiene, cyclohexanone, cyclohexene, spiro-[4,5-decane] and hydrogenated or partially hydrogenated aromatic rings as described above.
  • optionally substituted means that a group may or may not be further substituted with one or more groups selected from alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, aryloxy, aryloxyalkyl, benzyloxy, haloalkoxy, haloalkenyloxy, haloaryloxy, isocyano, cyano, formyl, carboxyl, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, amino, alkylamino, dialkylamino, alkenylamino, alkynylamino, arylamino, diarylamino, benzylamino, imino, alkylimino, alkenylimino, alkeny
  • Q is an optionally substituted Ci-C ⁇ alkyl group. More preferably Q is an - alkyl group.
  • one or more of the R groups on compounds of formula (II) represents or includes at least one reactive functionality, for example, acid, alcohol, amine, etc.
  • Such functionalities can be protected according to standard protection group chemistry. (See Greene and Wutz, "Protective Group Chemistry", 3 rd Edition, 1999, John Wiley & Sons.)
  • acid sensitive protecting groups like methoxymethyl (MOM) and benzyloxymethyl (BOM) ethers, are not susceptible to cleavage.
  • the present process is amenable to the preparation of esters of diboronic acid which have acid sensitive groups.
  • the term "liberated” refers to the process by which the produced HNR'R" is removed from the reaction process.
  • the liberation of the volatile amine produced as a product in the present reaction can be achieved in a multitude of ways using standard laboratory equipment.
  • the amine product is produced at a reaction temperature which is greater than the boiling temperature of the amine.
  • the concept of "volatility” as used herein merely requires the resultant amine to have a boiling point which is lower than the boiling point of the reaction solvent.
  • the volatile amine can be liberated as a gas by passing a stream of inert gas into the reaction mixture. Preferably nitrogen is used for this purpose.
  • the volatile amine can also be removed under vacuum during the reaction.
  • the amine product can be easily collected. It can then be reused again to prepare further compound of formula I by the Brotherton method which has already been discussed.
  • the amine can be collected by distillation and direct condensation from the reaction mixture either at atmospheric or under reduced pressure. As such the process of the present invention also provides for the product amine to be readily collected and recycled as it is not converted to its hydrochloride salt
  • the process is preferably performed at a reaction temperature which is higher than the boiling point of the produced amine.
  • the reaction is performed at a temperature between 80°C-140°C.
  • the reaction temperature will be dependant on both the boiling points of the reaction solvent and resulting amine byproduct.
  • the reaction is performed in a refluxing solvent.
  • Preferred solvents are those which solubilise the reactants.
  • a further advantage of the present invention is that it is not solvent specific. The reaction works well in both non-polar and polar solvents.
  • Preferred solvents include toluene, xylene, heptane, dioxane, diethyl ether, dichloromethane, dimethyl sulphoxide, butyl acetate or benzene. More preferred solvents are toluene or xylene.
  • the process is carried out without a solvent.
  • the reactants are simply added together and heated for such a time as to produce the amine which is liberated as a gas.
  • the main advantage of this method stems from the absence of a solvent, as the volatile amine can be collected in a substantially pure state, that is, without any accompanying solvent.
  • a further advantage of the process of the present invention is that after the liberation of the volatile amine the reaction mixture contains essentially only the desired diboronic ester. Accordingly, the present process avoids the conventional steps of filtering off and washing the resultant ammonium salt.
  • the tetrakis(dialkylamino)diboron is added to a solution of diol (2 mol equivalent) in an appropriate solvent at room temperature or at ⁇ 5°C to 10°C below boiling point of the solvent.
  • the addition is carried out at room temperature, the mixture is then slowly heated.
  • a slow stream of nitrogen can be used to disperse RRNH.
  • the addition is carried at ⁇ 5°C to 10°C below boiling point of the solvent (after an induction time of about 5 to 120 seconds or even longer), a vigorous to mild evolution of RRNH is expected to occur.
  • the more vigorous the evolution of RR NH the faster the reaction.
  • the reactant solution can be filtered, for example on a No-2 sintered glass funnel.
  • the solution can then be analysed by GC to establish purity. Usually the purity ranges between 95 - 99%.
  • the solvent is then removed in vacuo to give the ester of the diboronic acid. Further purification may be accomplished using recrystallisation from an appropriate solvent or by chromatographic techniques.
  • Tetrakis(dimethylamino)diboron (FW: 197.926) (50.0 g, 0.2526 mol) was added neat within 10 minutes to a solution of pinacol (FW: 118.18) (60.0 g, 0.5077 mol) in toluene (250 mL) at room temperature. This mixture was then slowly heated to 85°C. Me 2 NH gas started to come off and after 20 minutes the temperature was slowly raised to 105°C and maintained for 30 minutes. A slow stream of nitrogen was used to disperse Me NH. The solution was filtered on a sintered glass funnel. The solution was analysed by GC (98.1 % pure; 0.15% pinacol was left).
  • Tetrakis(dimethylamino)diboron (3.96 g, 20 mmol) was added neat within one minute to a mixture of pinacol (4.72 g, 40 mmol) in heptane (20 mL) at 40°C. The temperature was raised to 98°C. After an induction period of 5 minutes a vigorous evolution of Me 2 NH resulted. The temperature was maintained for 30 minutes at 98° C. Heptane (-20 mL) was used to decant and wash the solid residues (-29 mg)*. The combined solution was subjected to a slow stream of nitrogen to disperse the Me 2 NH and some solvent (maximum volume 30 mL). GC revealed 97.7% purity.
  • the solution was allowed to stand at room temperature for 18 hours and 1 hour at 0° C.
  • a Pasteur pipette was used to remove the liquid from the crystals.
  • the crystals were dried in a steady stream of nitrogen and heptane was removed in vacuo to give a colourless solid of bis(pinacolato)diboron (4.60 g, 90.5 % of >98 % purity by GC).
  • the mother liquor was kept for further recrystallisations.
  • Tetrakis(dimethylamino)diboron (3.96 g, 20 mmol) was added neat (within one minute) to a mixture of pinacol (4.72 g, 40 mmol) in dioxane (20 mL) at 40°C. The temperature was raised to 100°C. After an induction period of -10 minutes a vigorous evolution of Me 2 NH resulted. The temperature was maintained for 30 minutes at 100°C. The solvent was removed on the rotary evaporator to give a quantitative yield of bis(pinacolato)diboron. The solid was dissolved in petroleum (60°C - 80°C) (40 mL) and hot filtered to remove residues (-100 mg).
  • the filtrate was further washed with petroleum (60°C - 80°C).
  • the combined solution was subjected to a slow stream of nitrogen to disperse Me 2 NH and some solvent (maximum volume 35 mL).
  • GC revealed 97.4% purity.
  • the solution was allowed to stand at room temperature for 18 hours and 1 hour at 0°C.
  • a Pasteur pipette was used to remove the liquid from the crystals.
  • the crystals were dried in a steady stream of nitrogen and the petroleum was removed in vacuo to give a colourless solid of bis(pinacolato)diboron (-4.6 g, 90 % of >99 % purity by GC).
  • the mother liquor was kept for further recrystallisations. Note: For this procedure, the reaction is somewhat sluggish to start.
  • Tetrakis(dimethylamino)diboron (1.00 g, 5.05 mmol) was added neat (within one minute) to a mixture of pinacol (1.20 g, 10.15 mmol) in diethyl ether (10 mL) at room temperature and stirred for 18 hours. Nitrogen was used to blow off Me 2 NH and diethyl ether removed Yield: quantitative 97% pure by GC. The aforementioned recrystallization procedure gave bis(pinacolato)diboron 99% pure by GC.
  • Tetrakis(dimethylamino)diboron (1.00 g, 5.05 mmol) was added neat (within one minute) to a mixture of pinacol (1.20 g, 10.15 mmol) in dichloromethane (10 mL) at room temperature and stirred for 18 hours. Fine, white needles precipitated. Addition of petroleum spirits (40°C-60°C) (50 mL) gave a further precipitate of (Me 2 NH + ) 2 CH 2 .2Cl ⁇ The clear solution was evaporated to dryness to give bis(pinacolato)diboron (1.12 g, 87.5% and 97.7% pure by GC). Although this method worked, it is not a preferred method.
  • Tetrakis(dimethylamino)diboron (0.50 g, 5.077 mmol) was added neat (within one minute) to a mixture of pinacol (0.60 g, 2.53 mmol) in dimethylsulfoxide (10 mL) at 80°C. and heated for 10 minutes at 110° C. The mixture allowed to stand for 18 hours at room temperature. Fine, white needles had precipitated.
  • Addition of petroleum spirits (40°C- 60°C) (5x 5 mL) extracted bis(pinacolato)diboron which was evaporated to dryness (0.37 g, 57.8% and 98.9% pure by GC). Some residual solvent (DMSO) makes this procedure less desirable for high purity production.
  • DMSO residual solvent
  • Tetrakis(dimethylamino)diboron (0.50 g, 2.53 mmol) was added neat (within one minute) to a mixture of pinacol (0.60 g, 5.08 mmol) in butyl acetate (5 mL) at 80°C and then heated to 110° C for 10 minutes. This mixture was kept 18 hours at room temperature. Nitrogen was used to blow off Me 2 NH and butyl acetate was removed. Crude yield: (0.61 g, 95.2%; 96% pure by GC). The usual recrystallization procedure gave bis(pinacolato)diboron (0.32g, 49.9%; 99% pure by GC). The mother liquor was kept for further recrystallisations. Some crystalline dimethyl acetamide as byproduct was also obtained.
  • Pinacol (4.72 g, 40 mmol) was heated to 50°C, whereby it melted. Tetrakis(dimethylamino)diboron (3.96 g, 20 mmol) was added to this melt (within two minutes) and thoroughly mixed. After five minutes at 50°C, the reaction temperature was raised to 100°C. During the heating process, a milkiness started to appear with the simultaneous evolution of Me 2 NH over a period of fifteen minutes. The reaction mixture had then totally solidified but was kept for a further 15 minutes at 100°C. A stream of nitrogen was used to remove Me 2 NH. Yield: 4.99 g, 98.3%, 98.3% pure of soluble material.
  • Example 2 The solid was dissolved in petroleum (60°C - 80°C) (40 mL) and filtered hot to remove residues (-290 mg). The filtered residue was further washed with petroleum (60°C - 80°C). The combined solution was subjected to a slow stream of nitrogen to evaporate some solvent (maximum volume 35 mL). The solution was allowed to stand at room temperature for 18 hours and 1 hour at 0°C. A Pasteur pipette was used to remove the liquid from the crystals. The crystals were dried in a steady stream of nitrogen and evacuated to remove any residual petroleum to give bis(pinacolato)diboron as a colourless solid (4.78 g, 94.2 % of >99 % purity by GC). The mother liquor was kept for further recrystallisations.
  • Example 2 Example 2
  • Tetrakis(dimethylamino)diboron (9.89 g, 52.65 mmol) was added to a solution of 2,2- dimethyl-l,3-propanediol [neopentylglycol] (10.42 g, 100 mmol) in toluene (40 mL) at room temperature within two minutes. The mixture was heated to 105°C and an evolution of dimethylamine started to occur at 85°C. The mixture was heated for 60 minutes at 105°C then the toluene was removed to give a white solid: 11.39 g, 95.8%.
  • Hexyleneglycol (2-methyl-2,4-pentanediol) (FW: 118.18. 12.0 g, 101.6 mmol) in toluene (40 mL) was treated with tetrakis(dimethylamino)diboron (FW: 197.926; 9.9 g, 50 mmol) at room temperature and the reaction mixture stirred. The temperature was raised to 100°C within 10 minutes while the release of dimethylamine started to occur after about 5 minutes. The temperature was maintained at 100°C. for 60 minutes at which time for 30 minutes the evolution of dimethylamine occurred. Toluene was removed to give a solid (99.6% pure by GC).
  • (+)-Pinanediol (5.00 g, 29.37 mmol) in toluene (20 mL) was heated to 50°C and treated with tetrakis(dimethylamino)diboron (2.90 g, 14.65 mmol) within two minutes.
  • This mixture was then slowly heated to 100°C. and after an induction period of about 5 minutes evolution of Me 2 NH gas commenced. The mixture was maintained at 100°C. for 30 minutes. A slow stream of nitrogen was used to disperse Me 2 NH.
  • Diisopropyl D-tartrate (FW: 234.25; 2.34 g, 9.99 mmol) in toluene (20 mL) was heated to 100° C.
  • Tetrakis(dimethylamino)diboron (1.0 g, 5.05 mmol) was added neat within 2 minutes to this solution. After an induction period of about 10 minutes a slow release of Me 2 NH was observed. The mixture was kept at 100°C for 60 minutes. The solution was cooled to room temperature and analysed by GC and shown to be 78.8% pure.
  • This compound was prepared in accordance with the method described.

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Abstract

L'invention concerne un procédé de préparation d'ester d'acide diboronique qui consiste à faire réagir du tetrakis(dialkylamino)dibore avec un alcool pour obtenir ledit ester et une dialkylamine volatile, cette dernière s'échappant du mélange réactionnel sous forme gazeuse.
PCT/AU2004/000255 2003-02-28 2004-02-27 Preparation d'esters diboroniques WO2004076467A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102558209A (zh) * 2012-01-11 2012-07-11 海门瑞一医药科技有限公司 联硼酸频那醇酯生产工艺
CN102617623A (zh) * 2012-03-05 2012-08-01 凯莱英医药集团（天津）股份有限公司 一种合成联硼酸频哪醇酯的方法
WO2013014579A1 (fr) * 2011-07-22 2013-01-31 Basf Se Procédé pour la borylation d'organohalogénures
CN103183694A (zh) * 2012-11-30 2013-07-03 大连联化化学有限公司 新戊二醇基二硼的制备方法
CN116655674A (zh) * 2023-01-16 2023-08-29 中国科学院兰州化学物理研究所 一种合成高丰度硼10同位素的联硼酸酯的方法

Citations (2)

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US3062823A (en) * 1959-04-27 1962-11-06 United States Borax Chem Method for making organoboron compounds
US6603004B2 (en) * 1997-09-08 2003-08-05 Commonwealth Scientific And Industrial Research Organisation Process for preparing organic boronic acid derivatives using diboronic acid

Patent Citations (2)

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US3062823A (en) * 1959-04-27 1962-11-06 United States Borax Chem Method for making organoboron compounds
US6603004B2 (en) * 1997-09-08 2003-08-05 Commonwealth Scientific And Industrial Research Organisation Process for preparing organic boronic acid derivatives using diboronic acid

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NAKAMURA H. ET AL.: "A concise synthesis of enantiometrically pure L-(4-boronophenyl)alanine from L-tyrosine", J. ORG. CHEM., vol. 63, 1998, pages 7529 - 7530 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013014579A1 (fr) * 2011-07-22 2013-01-31 Basf Se Procédé pour la borylation d'organohalogénures
CN102558209A (zh) * 2012-01-11 2012-07-11 海门瑞一医药科技有限公司 联硼酸频那醇酯生产工艺
CN102617623A (zh) * 2012-03-05 2012-08-01 凯莱英医药集团（天津）股份有限公司 一种合成联硼酸频哪醇酯的方法
CN103183694A (zh) * 2012-11-30 2013-07-03 大连联化化学有限公司 新戊二醇基二硼的制备方法
CN116655674A (zh) * 2023-01-16 2023-08-29 中国科学院兰州化学物理研究所 一种合成高丰度硼10同位素的联硼酸酯的方法
CN116655674B (zh) * 2023-01-16 2024-04-16 中国科学院兰州化学物理研究所 一种合成高丰度硼10同位素的联硼酸酯的方法

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