CN111606785B - 一种光介导铜催化制备芳基内炔烃类化合物的方法 - Google Patents

一种光介导铜催化制备芳基内炔烃类化合物的方法 Download PDF

Info

Publication number
CN111606785B
CN111606785B CN202010632714.XA CN202010632714A CN111606785B CN 111606785 B CN111606785 B CN 111606785B CN 202010632714 A CN202010632714 A CN 202010632714A CN 111606785 B CN111606785 B CN 111606785B
Authority
CN
China
Prior art keywords
aryl
reaction
salt
catalysis
alkyne compound
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
CN202010632714.XA
Other languages
English (en)
Other versions
CN111606785A (zh
Inventor
梁磊
李仁龙
王松林
牛红英
谷永庆
李长恭
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.)
Henan Institute of Science and Technology
Original Assignee
Henan Institute of Science and 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 Henan Institute of Science and Technology filed Critical Henan Institute of Science and Technology
Priority to CN202010632714.XA priority Critical patent/CN111606785B/zh
Publication of CN111606785A publication Critical patent/CN111606785A/zh
Application granted granted Critical
Publication of CN111606785B publication Critical patent/CN111606785B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • 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
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
    • C07J1/0051—Estrane derivatives
    • C07J1/0059—Estrane derivatives substituted in position 17 by a keto group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明涉及一种光介导铜催化制备芳基内炔烃类化合物的方法，属于有机化学领域。以芳基硫盐和端炔烃为原料，以+1价铜盐为催化剂，碳酸钾作为碱，在DMSO等溶剂中反应得到芳基内炔烃类化合物，收率50％‑86％。该合成方法原料易得，反应条件温和条件，提供了一种简便、绿色、高效的内炔烃类化合物的合成途径，为含有芳香环药物分子引入炔基的有效方法。

Description

一种光介导铜催化制备芳基内炔烃类化合物的方法
技术领域
本发明涉及一种合成内炔烃类化合物的新方法，具体涉及一种光介导铜催化制备芳基内炔烃类化合物的方法，属于有机化学中过渡金属催化合成领域。
背景技术
芳基炔是一类重要的合成砌块，常应用于医药、大环、分子有机材料和天然产物的合成中。尤其在具有较为复杂分子结构的大环分子构筑中，显示出了难以代替的应用价值。经过长时间的发展，Sonogashira反应类型得到了丰富，通过筛选催化体系和改变芳基化试剂，多种合成新方法被开发出来，如下式所示：
Figure BDA0002566317770000011
第一类：以芳基碘或者芳基溴作为芳基化试剂，在钯盐或者钯盐/铜盐作为催化剂的偶联方法是Sonogashria偶联反应是构筑C(sp2)-C(sp)键的经典方法。其中铜(I)盐作为反应的副催化剂，可以提高反应速率。该反应的芳基化试剂为结构较为简单的芳基碘代物或者芳基溴代物，由于向芳香环上引入碘或者溴具有较大的挑战性，因此向分子结构较为复杂的芳香化合物中引入炔基将十分困难。同时，反应需要用到较为昂贵的钯盐作为催化剂。
第二/三类：以芳基重氮盐或者芳基季铵盐作为芳基化试剂，分别在金盐/光催化剂、钯盐/铜盐催化剂或者钯催化剂催化作用下，完成了C(sp2)-C(sp)键的构筑。该类型反应，芳基化试剂需要从芳香胺类化合物出发，将氨基转化为活性更高的官能团后进行偶联反应。该反应的芳基化试剂的种类受限于芳香胺类化合物，一定程度限制了产物的多样性。同时，反应需要用到较为昂贵钯盐作为催化剂。
第四类：以苯肼作为芳基化试剂，在钯盐催化作用下，完成了C(sp2)-C(sp)键的构筑。该类型反应，芳基化试剂的种类受限于苯肼类化合物，一定程度限制了产物的多样性。同时，反应需要用到较为昂贵的钯盐作为催化剂。
第五类：以芳基羧酸化合物作为芳基化试剂，在钯盐催化作用下，完成了C(sp2)-C(sp)键的构筑。该类型反应，芳基化试剂的种类受限于芳基羧酸类化合物，一定程度限制了产物的多样性。同时，反应需要用到较为昂贵的钯盐作为催化剂。
第六类：以芳基硫盐作为芳基化试剂，在钯盐/铜盐催化作用下，完成了C(sp2)-C(sp)键的构筑。该类型反应，芳基化试剂的种类较为丰富，可以普通芳香化合物出发来制备相应的硫盐。但是，反应仍然需要用到较为昂贵的钯盐作为催化剂。
发明内容
为了克服上述缺陷，本发明芳基化试剂采用来源更为丰富的硫盐作为芳基化试剂，在廉价铜盐催化下，在可见光催化下合成芳基内炔烃类化合物。该方法为芳基内炔烃类化合物提供了一种简便、绿色、高效的合成方法，丰富了Sonogashira反应类型。
一种光介导铜催化制备芳基内炔烃类化合物的方法，包括以下步骤：以芳基硫盐和端炔烃为原料，在Cu(I)盐催化和碱存在下，有机溶剂中可见光照射反应，得到芳基内炔烃类化合物。
反应方程式如下：
Figure BDA0002566317770000031
其中，Ar为苯基、取代苯基，取代苯基中取代基为卤素、羧酸酯、腈基、硝基、C1-C6烷基、C1-C6含杂原子烷基、C1-C6烷氧基、苯氧基、二甲胺基；X为BF4或OTf；R为C1-C6烷基、苯基、取代苯基、吡啶基、噻吩基、呋喃基，取代苯基中取代基为卤素、羧酸酯、腈基、硝基、C1-C6烷基、C1-C6含杂原子烷基、C1-C6烷氧基、苯氧基。
进一步地，在上述技术方案中，芳基硫盐选自：单取代芳基硫盐，双取代芳基硫盐，三取代芳基硫盐和芳香类药物硫盐。
进一步地，在上述技术方案中，Cu(I)盐选自CuCl、CuBr或CuI。
进一步地，在上述技术方案中，碱选自碳酸钾、磷酸钾或DBU。
进一步地，在上述技术方案中，所述芳基硫盐、端炔烃、Cu(I)盐与碱摩尔比为1:1.5-2.0:0.1-0.3:1-3。
进一步地，在上述技术方案中，有机溶剂选自二甲基亚砜、乙腈、N,N-二甲基甲酰胺，优选二甲基亚砜。
进一步地，在上述技术方案中，反应温度选自-10℃至30℃，优选30℃条件。
进一步地，在上述技术方案中，可见光源选自5-15W蓝色LED光。
进一步地，在上述技术方案中，整个反应过程需要惰性气体保护下操作，惰性气体优选氮气。
发明有益效果：
本发明提供了一种简便、绿色、高效、底物普适性广的芳基内炔烃类化合物的合成新方法，反应原料易得，反应条件温和条件，可降低能源的使用、减少对污染物排放，丰富了Sonogashira偶联反应的类型。
具体实施例
Figure BDA0002566317770000041
Figure BDA0002566317770000042
aReaction conditions:1a(0.2mmol),2a(0.3mmol),CuCl(10mol％)and K2CO3(0.6mmol)in DMSO(2.0mL)at 30℃ irradiation with 2*7W blue LED bulb underN2for 20h.bCuCl(10mol％),L4(12mol％).cYields of isolated product.
在反应条件的筛选过程中，首先考察了反应所需要的要素(entries 1-4)和不同溶剂、碱、和铜盐对反应的影响。通过以上筛选，可以说明该需要可见光的参与(entry 3)和铜盐作为催化剂(entry2)反应才可以发生。
实施例1：
Figure BDA0002566317770000051
在10mL反应管中，加入4-苯氧基芳基硫盐(1a,0.2mmol,94.4mg)、4-溴苯乙炔(2a,0.3mmol,54mg)、CuCl(2.0mg,0.02mmol)和K2CO3(82.9mg,0.6mmol)。加入完毕后，用塞子密封，经氮气置换3次后，用注射器向反应管内加入2mL二甲基亚砜。然后将反应至于蓝光LED反应箱内，反应管距光源10cm处搅拌反应20小时，经测量反应环境温度为30℃。TLC跟踪反应结束，将反应液通过湿法上样直接柱层析分离得到3aa,白色固体55.6mg，收率81％。M.p130.7-132.2℃。1H NMR(600MHz,CDCl3)δ7.50–7.48(m,4H),7.39–7.36(m,4H),7.16(t,J＝7.5Hz,1H),7.06(d,J＝7.8Hz,2H),6.98(d,J＝8.4Hz,2H).13C NMR(150MHz,CDCl3)δ158.0,156.5,133.4,133.1,131.7,130.0,124.1,122.5,122.5,119.7,118.5,117.5,90.3,87.9,77.2；HRMS(ESI):m/z calcd.For C20H14BrO+[M+H]+349.0223.found m/z 349.0215.
实施例2：
Figure BDA0002566317770000061
在10mL反应管中，加入氯贝特硫盐(1p,0.2mmol,109mg)、4-溴苯乙炔(2a,0.3mmol,54mg)、CuCl(2.0mg,0.02mmol)和K2CO3(82.9mg,0.6mmol)。加入完毕后，用塞子密封，经氮气置换3次后，用注射器向反应管内加入2mL二甲基亚砜。然后，将反应至于蓝光LED反应箱内，反应管距光源10cm处搅拌反应20小时，经测量反应环境温度为30℃。用TLC跟踪反应结束，将反应液通过湿法上样直接柱层析分离，得到3na，白色固体69.5mg，收率83％。M.p71.4-73.1℃；1H NMR(600MHz,CDCl3)δ7.50–7.47(m,2H),7.45–7.46(m,1H),7.39–7.35(m,2H),7.17(dd,J＝9.0,3.0Hz,1H),6.81(d,J＝9.0Hz,1H),4.25(q,J＝6.6Hz,2H),1.64(s,6H),1.27(t,J＝7.2Hz,3H).13C NMR(150MHz,CDCl3)δ173.9,155.2,133.1,132.7,131.8,129.3,127.4,122.9,122.3,112.0,118.4,93.2,86.4,81.0,77.4,77.2,77.0,61.7,25.4,14.2；HRMS(ESI):m/z calcd.For C20H18BrClNaO3 +[M+Na]+443.0020.found m/z443.0023.
实施例3：
Figure BDA0002566317770000062
在10mL反应管中，加入4-苯氧基芳基硫盐(1a，0.2mmol，94.4mg)、正丁炔(2o,0.4mmol,33mg)、CuCl(2.0mg,0.02mmol)和K2CO3(82.9mg,0.6mmol)。加入完毕后，用塞子密封，经氮气置换3次后，用注射器向反应管内加入2mL二甲基亚砜。然后将反应至于蓝光LED反应箱内，反应管距光源10cm处搅拌反应20小时，经测量反应环境温度为30℃。用TLC跟踪反应，终止反应后，将反应液通过湿法上样直接柱层析分离，得到3ao，浅黄色油状液体21.5mg，收率43％。1H NMR(600MHz,CDCl3)δ7.36–7.33(m,4H),7.12(t,J＝7.5Hz,1H),7.01(d,J＝7.8Hz,2H),6.91(d,J＝7.2Hz,2H),2.40(t,J＝6.9Hz,2H),1.61–1.56(m,2H),1.51–1.45(m,2H),0.95(t,J＝7.2Hz,3H).13C NMR(150MHz,CDCl3)δ156.9,156.9,133.2,130.0,123.7,119.3,119.0,118.6,89.8,80.1,77.2,31.0,22.2,19.2,13.8；HRMS(ESI):m/zcalcd.For C18H18NaO+[M+Na]+273.1250.found m/z273.1240.
实施例4
采用实施例2中类似的合成方法，得到如下化合物，其结构和收率分别如下：
Figure BDA0002566317770000071
Figure BDA0002566317770000081
以上实施例描述了本发明的基本原理、主要特征及优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。

Claims (4)

1.一种光介导铜催化制备芳基内炔烃类化合物的方法，其特征在于，包括以下步骤：以芳基硫盐和端炔烃为原料，在Cu(I)盐催化和碱存在下，二甲基亚砜中可见光照射反应，得到芳基内炔烃类化合物；反应方程式如下：
Figure FDA0003678269070000011
其中：Ar为苯基、取代苯基，取代苯基中取代基为卤素、羧酸酯、腈基、硝基、C1-C6烷基、C1-C6含杂原子烷基、C1-C6烷氧基、苯氧基、二甲胺基；X为BF4或OTf；R为C1-C6烷基、苯基、取代苯基、吡啶基、噻吩基、呋喃基，取代苯基中取代基为卤素、羧酸酯、腈基、硝基、C1-C6烷基、C1-C6含杂原子烷基、C1-C6烷氧基、苯氧基；碱选自碳酸钾或磷酸钾；反应温度选自-10℃至30℃；可见光源选自5-15W蓝色LED光。
2.根据权利要求1中所述光介导铜催化制备芳基内炔烃类化合物的方法，其特征在于：Cu(I)盐选自CuCl、CuBr或CuI。
3.根据权利要求1中所述光介导铜催化制备芳基内炔烃类化合物的方法，其特征在于：所述芳基硫盐、端炔烃、Cu(I)盐与碱摩尔比为1:1.5-2.0:0.1-0.3:1-3。
4.根据权利要求1中所述光介导铜催化制备芳基内炔烃类化合物的方法，其特征在于：反应在惰性气体保护下操作。
CN202010632714.XA 2020-07-02 2020-07-02 一种光介导铜催化制备芳基内炔烃类化合物的方法 Active CN111606785B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010632714.XA CN111606785B (zh) 2020-07-02 2020-07-02 一种光介导铜催化制备芳基内炔烃类化合物的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010632714.XA CN111606785B (zh) 2020-07-02 2020-07-02 一种光介导铜催化制备芳基内炔烃类化合物的方法

Publications (2)

Publication Number Publication Date
CN111606785A CN111606785A (zh) 2020-09-01
CN111606785B true CN111606785B (zh) 2022-08-09

Family

ID=72199054

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010632714.XA Active CN111606785B (zh) 2020-07-02 2020-07-02 一种光介导铜催化制备芳基内炔烃类化合物的方法

Country Status (1)

Country Link
CN (1) CN111606785B (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101890366A (zh) * 2010-07-01 2010-11-24 苏州大学 一种含二价铜盐的催化体系及其应用
CN102503748A (zh) * 2011-11-21 2012-06-20 苏州大学 一种用于薗头偶合反应的铜催化剂体系
CN103483383A (zh) * 2013-09-11 2014-01-01 南开大学 一种(1e,2e)-1,2-二(5-甲氧基-2-二苯基膦基苯亚甲基)肼的合成方法及应用
CN103864547A (zh) * 2014-03-31 2014-06-18 陕西师范大学 痕量1-卤代苯促进的CuI催化Sonogashira交叉偶联反应的方法
CN108610225A (zh) * 2018-03-12 2018-10-02 湖南科技大学 一种过渡金属催化硝基芳烃与末端芳基炔烃交叉偶联制备芳香炔烃的方法
WO2020094673A1 (en) * 2018-11-06 2020-05-14 Studiengesellschaft Kohle Mbh Reagents and process for direct c-h functionalization

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101890366A (zh) * 2010-07-01 2010-11-24 苏州大学 一种含二价铜盐的催化体系及其应用
CN102503748A (zh) * 2011-11-21 2012-06-20 苏州大学 一种用于薗头偶合反应的铜催化剂体系
CN103483383A (zh) * 2013-09-11 2014-01-01 南开大学 一种(1e,2e)-1,2-二(5-甲氧基-2-二苯基膦基苯亚甲基)肼的合成方法及应用
CN103864547A (zh) * 2014-03-31 2014-06-18 陕西师范大学 痕量1-卤代苯促进的CuI催化Sonogashira交叉偶联反应的方法
CN108610225A (zh) * 2018-03-12 2018-10-02 湖南科技大学 一种过渡金属催化硝基芳烃与末端芳基炔烃交叉偶联制备芳香炔烃的方法
WO2020094673A1 (en) * 2018-11-06 2020-05-14 Studiengesellschaft Kohle Mbh Reagents and process for direct c-h functionalization

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
铜催化Sonogashira交叉偶联反应的研究进展;关金涛等;《化学世界》;20120825(第08期);第508-512页 *

Also Published As

Publication number Publication date
CN111606785A (zh) 2020-09-01

Similar Documents

Publication Publication Date Title
Guo et al. Silver tungstate: a single-component bifunctional catalyst for carboxylation of terminal alkynes with CO 2 in ambient conditions
CN104803898B (zh) 芳基烷基、芳基芳基硫醚化合物及其合成方法
Yang et al. Copper (I) Iodide‐Catalyzed Sulfenylation of Maleimides and Related 3‐Indolylmaleimides with Thiols
CN114907370B (zh) 高纯度的噻吩并嘧啶化合物及其制备方法
CN106349147B (zh) 一种吡咯衍生物的合成方法
Zhang et al. Transition-metal-free decarboxylation of dimethyl malonate: an efficient construction of α-amino acid esters using TBAI/TBHP
CN106045991B (zh) 叶绿素作为光敏剂在可见光催化环化反应合成四氢喹啉衍生物中的应用
CN111606785B (zh) 一种光介导铜催化制备芳基内炔烃类化合物的方法
Wei et al. Microfluidic synthesis of pyrrolidin-2-ones via photoinduced organocatalyzed cyclization of styrene, α-bromoalkyl esters and primary amines
CN113929605A (zh) 一种邻位磺酰化芳胺化合物及其合成方法
CN113121403A (zh) 一种一步法制备三取代吲哚化合物的方法
CN109134320B (zh) 一种含β-羟基取代的磺酰类化合物的合成方法
CN108484552B (zh) 一种多取代3-苯并呋喃酮螺环己烯衍生物及其制备方法
WO2016197580A1 (zh) α-烷基支链取代的α-氨基酸衍生物的合成方法
CN114292153B (zh) 一种芳基卤化物的高效合成方法
CN110183341A (zh) 1,2-二羰基类化合物及其合成方法
CN112390696B (zh) 一种制备α-氨基腈的方法及其产品和应用
CN114075257B (zh) 一种由On-DNA芳基卤代物制备芳胺类化合物的方法
CN109438299B (zh) 一种苯磺酰肼类衍生物与三乙胺无金属催化合成苯磺酰烯胺类化合物的方法
CN113683658A (zh) 一种修饰蛋白质组氨酸残基的方法
CN113754544B (zh) 一种多取代(e)-三氟甲基烯烃的制备方法
CN110386929B (zh) 一种通过铜催化剂介导的杂环-杂环c-n交叉脱氢偶联反应方法
CN114057616B (zh) 一种合成n-取代苯磺酰胺类化合物的方法
CN108586406B (zh) 一种3-砜基香豆素化合物的制备方法
Vachlioti et al. Development of a multigram synthesis of the bradykinin receptor 2 agonist FR‐190997 and analogs thereof

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