CN114031475B - 一种溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法 - Google Patents

一种溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法 Download PDF

Info

Publication number
CN114031475B
CN114031475B CN202111594330.4A CN202111594330A CN114031475B CN 114031475 B CN114031475 B CN 114031475B CN 202111594330 A CN202111594330 A CN 202111594330A CN 114031475 B CN114031475 B CN 114031475B
Authority
CN
China
Prior art keywords
reaction
mmol
palladium
bromoarene
suzuki coupling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111594330.4A
Other languages
English (en)
Other versions
CN114031475A (zh
Inventor
许华建
刘赴粤
徐俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hefei University of Technology
Original Assignee
Hefei University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hefei University of Technology filed Critical Hefei University of Technology
Priority to CN202111594330.4A priority Critical patent/CN114031475B/zh
Publication of CN114031475A publication Critical patent/CN114031475A/zh
Application granted granted Critical
Publication of CN114031475B publication Critical patent/CN114031475B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/18—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving halogen atoms of halogenated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明公开了一种溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法，是以溴代芳烃和芳基硼酸为原料，纯水为溶剂，在碱、极低剂量催化剂存在下，添加溴单质即可以较高收率实现Suzuki偶联。本发明具有绿色安全、成本较低、操作简单、收率较高等优点。

Description

一种溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法
技术领域
本发明涉及一种溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法，在溴单质的促进作用下溴代芳烃和芳基硼酸发生Suzuki偶联合成联苯类化合物，属于有机合成领域。
背景技术
联芳基化合物是一类重要的结构基序，在医药、农药、功能性材料中有着重要的应用。常见的含有联苯结构的药物有抗高血压药沙坦联苯、消炎镇痛药氟比洛芬、以及治疗丙型肝炎病毒感染的药物雷迪帕韦等。
1979年，铃木章报道了在钯的催化下，芳基或烯基硼酸或硼酸酯与氯、溴、碘代芳烃或烯烃发生交叉偶联反应，即著名的Suzuki偶联反应[1]。该反应凭借其温和的反应条件、良好的官能团耐受性以及优异的产率一直是构建联芳基化合物的最重要的手段。因此，钯催化的铃木偶联反应在天然产物合成、医药、农药等领域有着广泛的应用。
迄今为止，绝大多数的Suzuki偶联反应使用的是金属钯作为催化剂，然而，金属钯昂贵的价格以及较强的毒性阻碍了该偶联反应在许多场合的应用。为了替代价格昂贵的钯，目前已经报道了许多其他金属催化的Suzuki-Miyaura交叉偶联反应，如Ni、Fe、Co、Cu等[2]。然而，这些过渡金属的使用仍然容易造成金属残留毒性和对环境的污染。为了响应绿色化学的号召、减少有害物质的释放，近年来，安全、价廉的反应介质－水被开发用于替代传统的有机溶剂实现Suzuki偶联。然而，大多数以水为介质的Suzuki反应依赖于较高催化量的贵金属催化剂的使用或微波、纳米材料负载等操作[3]。
参考文献：
[1]Miyaura,N.&Suzuki,A.Palladium-catalyzed cross-coupling reactionsof organoboron compounds.Chem.Rev.95,2457–2483(1995)
[2](a)Mastalir,M.,Stoger,B.,Pittenauer,E.,Allmaier,G.&Kirchner,K.Air-stable triazine-based Ni(ii)PNP pincer complexes as catalysts for the Suzuki–Miyauracross-coupling.Org.Lett.18,3186–3189(2016).(b)Shi,S.,Meng,G.&Szostak,M.Synthesis of biaryls through nickel-catalyzed Suzuki–Miyaura coupling ofamides by carbon–nitrogen bond cleavage.Angew.Chem.Int.Ed.55,6959–6963(2016).(c)Malapit,C.A.,Bour,J.R.,Brigham,C.E.&Sanford,M.S.Base-free nickel-catalyseddecarbonylative Suzuki–Miyaura coupling of acid fuorides.Nature 563,100–104(2018).(d)Tellis,J.C.,Primer,D.N.&Molander,G.A.Single-electrontransmetalation in organoboron cross-coupling by photoredox/nickel dualcatalysis.Science 345,433–436(2014).(e) Zhou,Y.,You,W.,Smith,K.B.&Brown,M.K.Copper-catalyzed cross coupling of boronic esters with aryl iodides andapplication to the carboboration of alkynes and allenes.Angew.Chem.Int.Ed.53,3475–3479(2014).
(f)Asghar,S.,Tailor,S.B.,Elorriaga,D.&Bedford,R.B.Cobalt-catalyzedSuzuki biaryl coupling of aryl halides.Angew.Chem.Int.Ed.56,16367–16370(2017).(g)Brien,H.M.O.Iron-catalysed substrate-directed Suzuki biaryl cross-coupling.Nat.Catal.1,429–437(2018).
[3](a)Handa,S.,Wang,Y.,Gallou,F.&Lipshutz,B.H.Sustainable Fe–ppmPdnanoparticle catalysis of Suzuki–Miyaura cross-couplings in water.Science349,1087–1091(2015).(b)Bai L,Wang J X,Microwave-promoted Palladium CatalyzedSuzuki Cross-coupling reaction in Water,Chin. Chem.Lett.15,286–287(2004).
发明内容
本发明针对现有合成方法的不足，提供了一种溴单质促进极低剂量钯催化的水相Suzuki 偶联反应方法，仅需使用极低剂量商业可得的钯源，即可以较高的收率实现偶联反应，极大地减少了金属残留毒性和催化剂成本，避免了有机溶剂的使用，具有绿色安全、稳定高效的优点。本方法具有绿色安全、稳定高效、操作简单、收率较高等优点。
本发明溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法，以溴代芳烃和芳基硼酸为原料，以纯水为溶剂，在碱、极低剂量催化剂存在下添加溴单质即可以较高产率实现Suzuki 偶联，分离提纯后得到联苯化合物。
具体是将液溴在氩气保护条件下溶于溶剂中，在溴代芳烃、芳基硼酸、催化剂、碱的存在下进行反应，反应结束后分离提纯得到目标产物。
所述溴代芳烃的结构式为：
其中：R为Me、OMe、CN、Ac等。
所述芳基硼酸的结构式为：
其中：R′为Me、Si(Me)3、t-Bu、Cl等；
所述芳基硼酸的添加量为溴代芳烃的1-3倍当量。
所述催化剂为双三苯基磷二氯化钯、氯化钯、双(二亚苄基丙酮)钯、[1,1'-双(二苯基膦基)二茂铁]二氯化钯、醋酸钯、三(二亚苄基丙酮)二钯、二(乙酰丙酮)钯、二氯二(三环己基膦)钯、四(三苯基膦)钯、三氟乙酸钯中的至少一种，催化剂的添加量为溴代芳烃的5ppm-500ppm倍当量。
所述碱为叔丁基醇钾、叔丁基醇锂、叔丁基醇钠、氢氧化钾、氢氧化钠、三乙胺、吡啶、甲醇锂、甲醇钠、碳酸铯、碳酸钾中的至少一种，添加量为溴代芳烃的1-4倍当量。
所述液溴的添加量为溴代芳烃的0.05-0.5倍当量。
本发明合成方法的反应温度为60-150℃，反应时间为6-12h；进一步优选反应温度为 110℃。
所述分离提纯是向反应液中加入水，用乙酸乙酯萃取，无水硫酸钠干燥，最后利用旋蒸除去溶剂，通过柱层析分离纯化，即可得到目标产物。
柱层析分离纯化时的洗脱液为石油醚：乙酸乙酯＝20:1～100:1，v/v。
本发明反应路线如下所示：
本发明的有益效果体现在：
1、本发明的合成方法绿色安全、成本较低、操作简单、易于后处理。
2、本发明的合成方法底物适用性广，产率比较高，副产物比较少，能兼容多种官能团。
具体实施方式
为进一步阐述本发明的特征和优点，下面结合具体的实施例对本发明的技术方案进行描述。但下列实施例仅为了进一步说明本发明，而不是限制本发明。
实施例1：
向装有磁力搅拌子25mL的高压氮保管中，加入原料4-溴苯乙酮(0.2mmol)、苯硼酸(0.3mmol)、碳酸钾(0.8mmol)，在氩气保护下加入2.0mL纯水、液溴(0.01mmol)、醋酸钯(2×10-6mmol)；将反应管固定于磁力搅拌器上，混合物110℃反应9h后，反应结束；向反应液中加入适量的乙酸乙酯萃取，无水硫酸钠干燥，最后利用旋蒸除去溶剂，粗产品经柱层析分离提纯得到目标产物(1c)，收率98％。该化合物的核磁数据为：1H NMR(600MHz, CDCl3)δ8.04(d,J＝8.3Hz,2H),7.71(d,J＝8.3Hz,2H),7.61(d,J＝7.2Hz,2H),7.48(t,J＝7.6 Hz,2H),7.41(t,J＝7.4Hz,1H),2.65(s,3H).13C NMR(151MHz,CDCl3)δ197.79,145.78, 139.84,135.82,128.96,128.91,128.23,127.27,127.23,26.68.
实施例2：
向装有磁力搅拌子25mL的高压氮保管中，加入原料3-甲氧基溴苯(0.2mmol)、4-甲基苯硼酸(0.3mmol)、碳酸钾(0.8mmol)，在氩气保护下加入2.0mL纯水、液溴(0.02mmol)、醋酸钯(1×10-5mmol)；将反应管固定于磁力搅拌器上，混合物110℃反应9h后，反应结束；向反应液中加入适量的乙酸乙酯萃取，无水硫酸钠干燥，最后利用旋蒸除去溶剂，粗产品经柱层析分离提纯得到目标产物(2c)，收率79％。该化合物的核磁数据为：1H NMR(400MHz, CDCl3)δ7.37(d,J＝7.9Hz,2H),7.21(t,J＝7.9Hz,1H),7.11(d,J＝7.9Hz,2H),7.05(d,J＝7.3Hz,1H),7.00(s,1H),6.75(dd,J＝8.0,2.1Hz,1H),3.71(s,3H),2.26(s,3H).13C NMR(101MHz, CDCl3)δ160.07,142.80,138.33,137.27,129.80,129.56,127.12,119.60,112.84,112.48,55.32, 21.18.
实施例3：
向装有磁力搅拌子25mL的高压氮保管中，加入原料3-氰基溴苯(0.2mmol)、1-萘硼酸 (0.3mmol)、碳酸钾(0.8mmol)，在氩气保护下加入2.0mL纯水、液溴(0.02mmol)、醋酸钯(1×10-5mmol)；将反应管固定于磁力搅拌器上，混合物110℃反应9h后，反应结束；向反应液中加入适量的乙酸乙酯萃取，无水硫酸钠干燥，最后利用旋蒸除去溶剂，粗产品经柱层析分离提纯得到目标产物(3c)，收率82％。该化合物的核磁数据为：1H NMR(400MHz, CDCl3)δ7.92(dd,J＝11.3,4.7Hz,2H),7.80–7.78(m,1H),7.76–7.71(m,3H),7.60(dd,J＝11.5,4.0Hz,1H),7.56–7.50(m,2H),7.47(ddd,J＝8.3,6.8,1.5Hz,1H),7.38(dd,J＝7.1,1.2Hz,1H).13C NMR(101MHz,CDCl3)δ142.14,137.76,134.58,133.88,133.57,131.21,131.01,129.27,128.78,128.63,127.24,126.75,126.25,125.44,125.22,118.90,112.69.
实施例4：
向装有磁力搅拌子25mL的高压氮保管中，加入原料对溴甲苯(0.2mmol)、4-三甲硅基苯硼酸(0.3mmol)、碳酸钾(0.8mmol)，在氩气保护下加入2.0mL纯水、液溴(0.01mmol)、醋酸钯(4×10-6mmol)；将反应管固定于磁力搅拌器上，混合物110℃反应9h后，反应结束；向反应液中加入适量的乙酸乙酯萃取，无水硫酸钠干燥，最后利用旋蒸除去溶剂，粗产品经柱层析分离提纯得到目标产物(4c)，收率85％。该化合物的核磁数据为：1H NMR(600MHz, CDCl3)δ7.62(m,4H),7.53(d,J＝7.9Hz,2H),7.27(d,J＝7.8Hz,2H),2.41(s,3H),0.34(s, 9H).13CNMR(151MHz,CDCl3)δ141.54,138.84,138.30,137.07,133.77,129.49,127.01,126.31,21.11,-1.05.
实施例5：
向装有磁力搅拌子25mL的高压氮保管中，加入原料4-溴苯乙酮(0.2mmol)、4-氯苯硼酸(0.3mmol)、碳酸钾(0.8mmol)，在氩气保护下加入2.0mL纯水、液溴(0.02mmol)、醋酸钯(2×10-6mmol)；将反应管固定于磁力搅拌器上，混合物110℃反应9h后，反应结束；向反应液中加入适量的乙酸乙酯萃取，无水硫酸钠干燥，最后利用旋蒸除去溶剂，粗产品经柱层析分离提纯得到目标产物(5c)，收率95％。该化合物的核磁数据为：1H NMR(600 MHz,CDCl3)δ8.11–7.96(m,2H),7.68–7.61(m,2H),7.58–7.50(m,2H),7.47–7.39(m,2H), 2.63(s,3H).13C NMR(151MHz,CDCl3).δ197.65,144.53,138.38,136.20,134.54,129.23,129.08,128.58,127.14,26.73.
实施例6：
向装有磁力搅拌子25mL的高压氮保管中，加入原料对溴苯酚(0.2mmol)、4-甲基苯硼酸(0.3mmol)、碳酸钾(0.8mmol)，在氩气保护下加入2.0mL纯水、液溴(0.02mmol)、醋酸钯(1×10-5mmol)；将反应管固定于磁力搅拌器上，混合物110℃反应9h后，反应结束；向反应液中加入适量的乙酸乙酯萃取，无水硫酸钠干燥，最后利用旋蒸除去溶剂，粗产品经柱层析分离提纯得到目标产物(6c)，收率83％。该化合物的核磁数据为：1H NMR(500 MHz,CDCl3)δ2.36(s,3H),4.93(s,1H),6.61(d,J＝8.5Hz,2H),6.87(d,J＝8.5Hz,1H),7.22(d, J＝8.0Hz,1H),7.43(dd,J＝8.6,8.53Hz,2H),7.51(d,J＝8.5Hz,2H).13C NMR(125MHz, CDCl3)δ21.1,115.7,126.4,128.1,129.5,133.7,136.5,137.5,155.4.
实施例7：
向装有磁力搅拌子25mL的高压氮保管中，加入原料对溴甲苯(0.2mmol)、3，4，5-三甲氧基苯硼酸(0.3mmol)、碳酸钾(0.8mmol)，在氩气保护下加入2.0mL纯水、液溴(0.02mmol)、醋酸钯(2×10-5mmol)；将反应管固定于磁力搅拌器上，混合物110℃反应9h后，反应结束；向反应液中加入适量的乙酸乙酯萃取，无水硫酸钠干燥，最后利用旋蒸除去溶剂，粗产品经柱层析分离提纯得到目标产物(7c)，收率89％。该化合物的核磁数据为：1HNMR(400MHz,CDCl3)δ7.45(d,J＝8.2Hz,2H),7.24(d,J＝7.8Hz,2H),6.76(s,2H),3.92(s,6H),3.89(s, 3H),2.39(s,3H).13CNMR(101MHz,CDCl3)δ153.43,138.50,137.43,137.20,137.11,129.45, 126.93,104.29,60.96,56.18,21.09.
实施例8：
向装有磁力搅拌子25mL的高压氮保管中，加入原料对溴甲苯(0.2mmol)、4-叔丁基苯硼酸(0.3mmol)、碳酸钾(0.8mmol)，在氩气保护下加入2.0mL纯水、液溴(0.01mmol)、醋酸钯(1×10-5mmol)；将反应管固定于磁力搅拌器上，混合物110℃反应9h后，反应结束；向反应液中加入适量的乙酸乙酯萃取，无水硫酸钠干燥，最后利用旋蒸除去溶剂，粗产品经柱层析分离提纯得到目标产物(8c)，收率90％。该化合物的核磁数据为：1HNMR(400MHz, CDCl3)δ7.48(dt,J＝14.9,8.4Hz,6H).,7.23(t,J＝3.9Hz,2H),2.38(s,3H),1.36(s, 9H).13CNMR(101MHz,CDCl3)δ149.93,138.25,138.19,136.68,129.41,126.85,126.59,125.65,34.49,31.38,21.09。

Claims (4)

1.一种溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法，其特征在于：
以溴代芳烃和芳基硼酸为原料，以纯水为溶剂，将液溴在氩气保护条件下溶于溶剂中，在溴代芳烃、芳基硼酸、催化剂、碱的存在下进行反应，反应温度为60-150℃，反应时间为6-12h，反应结束后分离提纯得到目标产物；
反应路线如下所示：
其中：R为Me、OMe、CN或Ac；R′为Me、Si(Me)3、t-Bu或Cl；
所述芳基硼酸的添加量为溴代芳烃的1-3倍当量；
所述催化剂为醋酸钯，催化剂的添加量为溴代芳烃的5ppm-500ppm倍当量；
所述液溴的添加量为溴代芳烃的0.05-0.5倍当量。
2.根据权利要求1所述的方法，其特征在于：
所述碱为叔丁基醇钾、叔丁基醇锂、叔丁基醇钠、氢氧化钾、氢氧化钠、三乙胺、吡啶、甲醇锂、甲醇钠、碳酸铯、碳酸钾中的至少一种，添加量为溴代芳烃的1-4倍当量。
3.根据权利要求1所述的方法，其特征在于：
所述分离提纯是向反应液中加入水，用乙酸乙酯萃取，无水硫酸钠干燥，最后利用旋蒸除去溶剂，通过柱层析分离纯化，即可得到目标产物。
4.根据权利要求3所述的方法，其特征在于：
柱层析分离纯化时的洗脱液为石油醚：乙酸乙酯＝20:1～100:1，v/v。
CN202111594330.4A 2021-12-24 2021-12-24 一种溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法 Active CN114031475B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111594330.4A CN114031475B (zh) 2021-12-24 2021-12-24 一种溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111594330.4A CN114031475B (zh) 2021-12-24 2021-12-24 一种溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法

Publications (2)

Publication Number Publication Date
CN114031475A CN114031475A (zh) 2022-02-11
CN114031475B true CN114031475B (zh) 2023-11-21

Family

ID=80147229

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111594330.4A Active CN114031475B (zh) 2021-12-24 2021-12-24 一种溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法

Country Status (1)

Country Link
CN (1) CN114031475B (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5177258A (en) * 1991-05-22 1993-01-05 Bromine Compounds, Ltd. Method of production of biaryl derivatives
CN101143331A (zh) * 2007-09-06 2008-03-19 苏州大学 一种用于偶联反应的非钯催化剂体系
CN102351620A (zh) * 2011-08-09 2012-02-15 太原理工大学 一种纳米钯催化剂催化Suzuki偶联反应制备联苯类化合物的方法
CN102617256A (zh) * 2012-02-29 2012-08-01 大连理工大学 一种在纯水中制备联芳类化合物的方法
CN102964190A (zh) * 2012-12-03 2013-03-13 大连理工大学 一种在纯水中制备联芳类化合物的方法
WO2015063543A1 (en) * 2013-10-30 2015-05-07 Latvian Institute Of Organic Synthesis Hydridopalladium(ii) halides as preformed catalysts for suzuki-miyaura cross-coupling reactions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5177258A (en) * 1991-05-22 1993-01-05 Bromine Compounds, Ltd. Method of production of biaryl derivatives
CN101143331A (zh) * 2007-09-06 2008-03-19 苏州大学 一种用于偶联反应的非钯催化剂体系
CN102351620A (zh) * 2011-08-09 2012-02-15 太原理工大学 一种纳米钯催化剂催化Suzuki偶联反应制备联苯类化合物的方法
CN102617256A (zh) * 2012-02-29 2012-08-01 大连理工大学 一种在纯水中制备联芳类化合物的方法
CN102964190A (zh) * 2012-12-03 2013-03-13 大连理工大学 一种在纯水中制备联芳类化合物的方法
WO2015063543A1 (en) * 2013-10-30 2015-05-07 Latvian Institute Of Organic Synthesis Hydridopalladium(ii) halides as preformed catalysts for suzuki-miyaura cross-coupling reactions

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Br2促进的低负载钯催化的水相Suzuki偶联反应研究;刘赴粤;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第06期);1-139 *
Iodine-Catalyzed Suzuki–Miyaura Coupling Performed in Air;Jincheng Mao 等;《Adv. Synth. Catal.》;第351卷;第635页摘要以及第637页表1 *
Nickel(0) powder catalysis in Suzuki–Miyaura cross-coupling reaction;Chan Sik Cho 等;《Catalysis Communications》;第11卷;第191–195页 *

Also Published As

Publication number Publication date
CN114031475A (zh) 2022-02-11

Similar Documents

Publication Publication Date Title
Boruah et al. A novel green protocol for ligand free Suzuki–Miyaura cross-coupling reactions in WEB at room temperature
Lei et al. Arylation of unactivated arenes
Jin et al. Highly Active, Well‐Defined (Cyclopentadiene)(N‐heterocyclic carbene) palladium Chloride Complexes for Room‐Temperature Suzuki–Miyaura and Buchwald–Hartwig Cross‐Coupling Reactions of Aryl Chlorides and Deboronation Homocoupling of Arylboronic Acids
Shi et al. A new dimeric bidentated NHC–Pd (II) complex from trans-cyclohexane-1, 2-diamine for Suzuki reaction and Heck reaction
Wang et al. CuI-catalyzed Suzuki coupling reaction of organoboronic acids with alkynyl bromides
Simeone et al. Palladium on carbon as a precatalyst for the Suzuki–Miyuara cross-coupling of aryl chlorides
Shen et al. Bidentate auxiliary-directed alkenyl C–H allylation via exo-palladacycles: synthesis of branched 1, 4-dienes
Jones et al. Gold compounds as efficient co-catalysts in palladium-catalysed alkynylation
Gohain et al. Preparation of phenolic compounds through catalyst-free ipso-hydroxylation of arylboronic acids
EP3315486B1 (en) Method for producing aromatic compound
Xu et al. Suzuki-Miyaura cross-coupling reaction of aryl chlorides with aryl boronic acids catalyzed by a palladium dichloride adduct of N-diphenylphosphanyl-2-aminopyridine
Ren et al. Iron-catalyzed conversion of unactivated aryl halides to phenols in water
Shabalin et al. The influence of the nature of phosphine ligand on palladium catalysts for cross-coupling of weakly nucleophilic potassium pentafluorophenyltrifluoroborate with ArHal and PhCH2Hal (Hal= Br, Cl)
Zhang et al. Palladacycle as highly efficient catalyst for ring opening of oxabicyclic alkenes with organozinc halides
Zhang et al. Nickel-and Palladium-Catalyzed Cross-Coupling of Stibines with Organic Halides: Site-Selective Sequential Reactions with Polyhalogenated Arenes
Mboyi et al. Straightforward synthesis of substituted dibenzyl derivatives
CN114031475B (zh) 一种溴单质促进极低剂量钯催化的水相Suzuki偶联反应方法
Ogawa et al. Palladium-free synthesis of unsymmetrical diarylethynes by cross-coupling reaction of alkynylboronates with aryl iodides catalyzed by CuCl
Dilauro et al. Cobalt-catalyzed cross-coupling reactions of aryl-and alkylaluminum derivatives with (hetero) aryl and alkyl bromides
Xu et al. Iron‐Catalyzed Room Temperature Cross‐Couplings of Bromophenols with Aryl Grignard Reagents
Wang et al. An Easily Prepared Tetraphosphine and Its Use in the Palladium-Catalyzed Suzuki–Miyaura Coupling of Aryl Chlorides
Silveira et al. Homocoupling of aryl iodides and bromides promoted by sulfur-containing palladacycles
Qin et al. Palladium-catalyzed carbonylative cross-coupling reaction of triarylantimony dicarboxylates with arylboronic acids: Synthesis of biaryl ketones
CN100588656C (zh) 钳形双咪唑啉钯化合物及其在Suzuki反应中的应用
CN102139229B (zh) 一种负载型金催化剂的制备方法及其应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant