CN117466694A - 一种构建季碳中心的方法 - Google Patents

一种构建季碳中心的方法 Download PDF

Info

Publication number
CN117466694A
CN117466694A CN202311376023.8A CN202311376023A CN117466694A CN 117466694 A CN117466694 A CN 117466694A CN 202311376023 A CN202311376023 A CN 202311376023A CN 117466694 A CN117466694 A CN 117466694A
Authority
CN
China
Prior art keywords
quaternary carbon
carbon center
katritzky
constructing
salt
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.)
Pending
Application number
CN202311376023.8A
Other languages
English (en)
Inventor
徐文涛
蔡露兰
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.)
Nanchang University
Original Assignee
Nanchang University
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 Nanchang University filed Critical Nanchang University
Priority to CN202311376023.8A priority Critical patent/CN117466694A/zh
Publication of CN117466694A publication Critical patent/CN117466694A/zh
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32Preparation 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
    • C07C1/321Preparation 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
    • C07C1/323Preparation 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 the hetero-atom being a nitrogen atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/26Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/18Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic 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
    • C07D213/02Heterocyclic 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
    • C07D213/04Heterocyclic 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
    • C07D213/06Heterocyclic 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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16Heterocyclic 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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D239/00Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D241/00Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Landscapes

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

Abstract

本发明提供了一种构建季碳中心的方法,属于有机化学技术领域。本发明方法为:在溶剂与氮气氛围下,三苯乙酸在碳酸氢钾的作用下脱去质子,随后再脱去二氧化碳生成三苯基负离子作为亲核剂进攻作为烷基化试剂的Katritzky盐,以良好的产率得到含季碳中心的产物。本发明从稳定易制备的Katritzky盐和三级羧酸直接构建季碳中心,不需要氧化剂以及高温条件,同时避免了过渡金属的使用,工艺操作简便、反应条件要求低、对环境友好。

Description

一种构建季碳中心的方法
技术领域
本发明属于有机化学技术领域,具体涉及一种构建季碳中心的方法。
背景技术
季碳立体中心的化合物结构更具有多样性和刚性,因此季碳中心广泛存在于药物、天然产物等生物活性化合物中,在生物医学、药学领域具有重要地位[参见:Hervieu,C.;Kirillova,M.S.;Suarez,T.;Muller,M.;Merino,E.;Nevado,C.Nat Chem 2021,13,327.]。例如,在2011年,美国销售额前200名的药中,有12%具有季碳手性中心。发展高效的构建季碳手性中心的方法有助于合成这些生物活性分子及其类似物,研究结构和功能的关系,从而促进新药研发。但由于受位阻拥挤、构象柔性等影响,构建季碳立体中心在有机合成中一直是一个巨大的挑战[参见:Zeng,X.P.;Cao,Z.Y.;Wang,Y.H.;Zhou,F.;Zhou,J.Chem.Rev.2016,116,7330.]。
构建季碳可以通过烷基化手段来引入碳,常见的各种烷基化试剂(如烷基卤、羧酸、酯类等)发展都比较成熟,我们选择近五年科学家研究热点的Katritzky盐作为烷基化试剂,Katritzky盐以在自然界存在广泛的胺为合成原料,是一种很好的烷基化试剂[参见:Plunkett,S.;Basch,C.H.;Santana,S.O.;Watson,M.P.J.Am.Chem.Soc.2019,141,2257.]。通过亲核取代反应,选择酸和Katritzky盐作为底物,酸脱羧后作为亲核试剂进攻Katritzky盐构建季碳中心,该反应条件环境友好、操作简单。
发明内容
针对背景所提内容,本发明的目的在于提供一种构建季碳中心的方法。
本发明反应合成路线如下:
本发明提供了一种构建季碳中心的方法,包括如下步骤::
步骤一、取Katritzky盐与2,2,2-三苯乙酸混合,再加入碳酸氢钾,混合物在氮气氛围下加至溶剂中;
步骤二、步骤一体系在室温下搅拌反应,反应结束加水淬灭,用乙酸乙酯萃取,有机层浓缩层析得到产物。
作为优选,Katritzky盐中的R1、R2基团分别为各种取代的芳基、烷基、氢。
作为优选,Katritzky盐中的R1基团是各种取代的芳基时,R2为氢。
作为优选,Katritzky盐中的R1基团是-C10H13时,R2为甲基。
作为优选,步骤一所述Katritzky盐、2,2,2-三苯乙酸和碳酸氢钾的物质的量之比为1:1:1。
作为优选,步骤一所述溶剂为0.2M的二甲基亚砜(DMSO)。
作为优选,步骤二搅拌反应时间为6h。
典型反应如下:
本发明的有益效果为:
本发明的方法反应条件温和,不需要氧化剂以及高温条件,同时避免了过渡金属的使用,从稳定易制备的Katritzky盐和三级羧酸直接构建季碳中心。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将结合实施例对本发明的技术方案进行清楚、完整地描述。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
除非另有定义,本文所使用的所有技术和科学术语与本发明技术领域的技术人员通常理解的含义相同。在本发明的说明书所使用的术语只是为了描述具体实施例的目的,并非用于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
实施例所用原料Katritzky盐的合成:
根据Watson及其同事描述的程序[参见:Plunkett,S.;Basch,C.H.;Santana,S.O.;Watson,M.P.J.Am.Chem.Soc.2019,141,2257.],将2,4,6-三苯基四氟硼酸吡啶鎓(1.0equiv)和胺(1.2equiv)加入到含有搅拌棒的Schlenk中。随后加入干燥的EtOH(1.0M),导致颜色从黄色变为黑橙色。然后搅拌混合物,并在90℃的油浴中回流加热5h。此时,将混合物冷却至室温。然后加入Et2O(15mL)并剧烈振荡,形成固体沉淀物。过滤由此获得的固体,用Et2O(2×15mL)洗涤,并在高真空下干燥。如果吡啶鎓盐未能沉淀,则进行快速柱色谱,用DCM/丙酮混合物洗脱。
实施例1
称取(48.5mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到28.2mg产物/>(石油醚:乙酸乙酯=50:1),产率84%,1H NMR(400MHz,CDCl3)δ7.2–7.1(m,15H),7.0(t,J=7.4Hz,1H),7.0(t,J=7.5Hz,2H),6.6(d,J=7.6Hz,2H),3.9(s,2H)。
实施例2
称取(49.2mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到25.8mg产物(石油醚:乙酸乙酯=50:1),产率74%,1H NMR(400MHz,CDCl3)δ7.2(dd,J=4.4,1.2Hz,11H),7.2–7.1(m,3H),7.2–7.1(m,1H),6.8(d,J=7.7Hz,2H),6.5(d,J=7.7Hz,2H),3.9(s,2H),2.2(s,3H);13C NMR(101MHz,CDCl3)δ146.7,135.4,135.3,131.0,129.8,128.0,127.5,125.9,58.4,45.9,20.9。
实施例3
称取(56.9mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到23.0mg产物(石油醚:乙酸乙酯=50:1),产率55%,1H NMR(400MHz,CDCl3)δ7.3–7.2(m,12H),7.2–7.1(m,3H),6.8(d,J=7.5Hz,2H),6.6(d,J=8.6Hz,2H),3.9(s,2H);13CNMR(101MHz,CDCl3)δ147.6(q,J=2.02Hz),146.3,137.3,132.2,129.7,127.7,126.1,119.7,118.2(q,J=216.1Hz),58.5,45.5。
实施例4
称取(59.9mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到20.2mg产物(石油醚:乙酸乙酯=50:1),产率58%,1H NMR(400MHz,CDCl3)δ7.2–7.1(m,15H),7.0(t,J=7.3Hz,1H),6.9(d,J=7.4Hz,1H),6.9(d,J=6.4Hz,1H),6.8(t,J=6.7Hz,1H),3.9(s,2H),1.5(s,3H);13C NMR(101MHz,CDCl3)δ146.5,138.8,137.1,130.2,129.9,129.7,127.5,126.0,125.9,125.0,58.2,41.6,19.2。
实施例5
称取(55.3mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到22.5mg产物(石油醚:乙酸乙酯=50:1),产率56%,1H NMR(400MHz,CDCl3)δ7.5(d,J=7.8Hz,1H),7.3–7.1(m,15H),7.1(d,J=7.6Hz,1H),7.0(q,J=8.0Hz,2H),4.3(s,2H);13CNMR(101MHz,CDCl3)δ146.7,137.9(q,J=1.01Hz),131.2(d,J=134.3Hz),130.5,129.7,127.8,126.3(q,J=3.03Hz),126.1,125.8(q,J=3.03Hz),125.6,122.0(q,J=216.1Hz),57.4,41.2(d,J=2.02Hz)。
实施例6
称取(51.9mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到25.0mg产物(石油醚:乙酸乙酯=50:1),产率68%,1H NMR(400MHz,CDCl3)δ7.3–7.2(m,12H),7.2(m,3H),7.0(d,J=8.7Hz,1H),6.9(t,J=7.8Hz,1H),6.5(d,J=9.9Hz,2H),3.9(s,2H);13C NMR(101MHz,CDCl3)δ146.2,140.5,133.0,131.2,129.7,129.2,128.4,127.7,126.1,126.1,58.5,45.9。
实施例7
称取(54.5mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到25.2mg产物(石油醚:乙酸乙酯=50:
1),产率64%,1H NMR(400MHz,CDCl3)δ7.2(d,J=4.1Hz,12H),7.2(h,J=4.1Hz,3H),6.2(s,1H),5.8(s,2H),3.9(s,2H),3.5(s,6H);13C NMR(101MHz,CDCl3)δ159.6,146.6,140.7,129.8,127.6,125.9,108.9,99.0,58.4,55.0,46.7。
实施例8
称取(53.7mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到22.0mg产物(石油醚:乙酸乙酯=50:1),产率57%,1H NMR(400MHz,CDCl3)δ7.3–7.1(m,15H),6.7(t,J=8.7Hz,1H),6.6–6.5(m,2H),3.8(s,2H);13C NMR(101MHz,CDCl3)δ156.6,(d,J=46.5Hz),146.1,135.4(d,J=4.0Hz),133.0,130.5(d,J=7.07Hz),129.6,128.8(d,J=10.1Hz),127.7,126.2,119.5(d,J=17.2Hz),115.2(d,J=21.2Hz),58.5,45.2。
实施例9
称取(49.1mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到23.5mg产物(石油醚:乙酸乙酯=40:1),产率69%,1H NMR(400MHz,CDCl3)δ7.2(m,J=7.7,7.0Hz,15H),6.9(d,J=5.1Hz,1H),6.7(t,J=4.1Hz,1H),6.3(d,J=3.4Hz,1H),4.1(s,2H);13C NMR(101MHz,CDCl3)δ146.5,140.7,129.6,127.9,127.7,126.2,125.7,124.3,58.1,41.8。
实施例10
称取(48.6mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到24.5mg产物(石油醚:乙酸乙酯=50:1),产率73%,1H NMR(400MHz,CDCl3)δ8.3(d,J=3.6Hz,1H),7.3(d,J=7.7Hz,6H),7.3–7.1(m,10H),6.9(dd,J=7.5,5.0Hz,1H),6.3(d,J=7.9Hz,1H),4.2(s,2H);13C NMR(101MHz,CDCl3)δ158.9,148.3,146.7,135.0,129.7,127.7,126.0,125.0,121.0,58.2,49.0。
实施例11
称取(50.0mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到26.5mg产物(石油醚:乙酸乙酯=10:1),产率76%,1H NMR(400MHz,CDCl3)δ7.3(d,J=7.8Hz,6H),7.2(dd,J=7.5Hz,6H),7.2(t,J=7.3Hz,3H),7.1(t,J=7.8Hz,1H),6.8(d,J=7.6Hz,1H),6.1(d,J=7.9Hz,1H),4.2(s,2H),2.4(s,3H);13C NMR(101MHz,CDCl3)δ158.1,156.7,146.8,135.3,129.8,127.6,125.9,121.7,120.3,58.1,49.0,24.3。
实施例12
称取(48.7mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到13.8mg产物/>(石油醚:乙酸乙酯=10:1),产率41%,1H NMR(400MHz,CDCl3)δ8.3(d,J=4.9Hz,2H),7.3(d,J=8.0Hz,6H),7.2(t,J=7.4Hz,6H),7.1(t,J=7.2Hz,3H),6.9(t,J=4.9Hz,1H),4.4(s,2H);13C NMR(101MHz,CDCl3)δ168.8,155.9,147.0,129.6,128.2,127.4,125.8,118.0,58.2,49.9。
实施例13
称取(48.7mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到19.8mg产物/>(石油醚:乙酸乙酯=10:1),产率59%,1H NMR(400MHz,CDCl3)δ8.3–8.3(m,1H),8.2(d,J=2.6Hz,1H),7.5(d,J=1.6Hz,1H),7.4–7.3(m,6H),7.3–7.2(m,6H),7.2–7.1(m,3H),4.2(s,2H);13CNMR(101MHz,CDCl3)δ154.9,146.4,146.2,143.0,141.6,129.5,127.8,126.2,58.4,46.3。
实施例14
称取(52.7mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到11.3mg产物(石油醚:乙酸乙酯=50:1),产率30%,1H NMR(400MHz,CDCl3)δ7.3(t,J=7.4Hz,5H),7.2(t,J=6.4Hz,7H),7.1(d,J=7.8Hz,6H),7.1–6.9(m,2H),3.3(dt,J=12.8,6.5Hz,1H),2.8(ddd,J=14.0,9.4,4.9Hz,1H),2.7–2.6(m,1H),2.1–1.9(m,1H),1.0(d,J=6.4Hz,3H),0.8(dtd,J=13.8,9.3,4.8Hz,1H);13C NMR(101MHz,CDCl3)δ142.3,129.4,129.4,128.7,128.3,126.9,126.2,125.8,61.9,35.3,35.1,34.2,16.1。
实施例15
称取(44.9mg,0.1mmol),2,2,2-三苯乙酸(28.8mg,0.1mmol),KHCO3(10.0mg,0.1mmol),加入反应管,通过真空管线抽换气三次,在氮气氛围下、DMSO(0.5mL)、室温反应6h。干法上样,柱层析(300-400目层析硅胶)得到29.1mg产物/>(石油醚:乙酸乙酯=50:1),产率98%,1H NMR(400MHz,CDCl3)δ7.2(dd,J=13.7,6.6Hz,12H),7.2–7.1(m,3H),4.7(s,1H),4.3(s,1H),3.4(s,2H),1.4(s,3H)。
以上所描述的实施例仅表达了本发明的几种优选实施例,其描述较为具体和详细,但并不用于限制本发明。应当指出,对于本领域的技术人员来说,本发明还可以有各种变化和更改,凡在本发明的构思和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

Claims (7)

1.一种构建季碳中心的方法,其特征在于,包括如下步骤:
步骤一、取Katritzky盐与2,2,2-三苯乙酸混合,再加入碳酸氢钾,混合物在氮气氛围下加至溶剂中;
步骤二、步骤一体系在室温下搅拌反应,反应结束加水淬灭,用乙酸乙酯萃取,有机层浓缩层析得到产物;
反应合成路线如下:
2.根据权利要求1所述的构建季碳中心的方法,其特征在于,Katritzky盐中的R1、R2基团分别为各种取代的芳基、烷基、氢。
3.根据权利要求1所述的构建季碳中心的方法,其特征在于,Katritzky盐中的R1基团是各种取代的芳基时,R2为氢。
4.根据权利要求1所述的构建季碳中心的方法,其特征在于,Katritzky盐中的R1基团是-C10H13时,R2为甲基。
5.根据权利要求1所述的构建季碳中心的方法,其特征在于,步骤一所述Katritzky盐、2,2,2-三苯乙酸和碳酸氢钾的物质的量之比为1:1:1。
6.根据权利要求1所述的构建季碳中心的方法,其特征在于,步骤一所述溶剂为0.2M的二甲基亚砜。
7.根据权利要求1所述的构建季碳中心的方法,其特征在于,步骤二搅拌反应时间为6h。
CN202311376023.8A 2023-10-23 2023-10-23 一种构建季碳中心的方法 Pending CN117466694A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311376023.8A CN117466694A (zh) 2023-10-23 2023-10-23 一种构建季碳中心的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311376023.8A CN117466694A (zh) 2023-10-23 2023-10-23 一种构建季碳中心的方法

Publications (1)

Publication Number Publication Date
CN117466694A true CN117466694A (zh) 2024-01-30

Family

ID=89635665

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311376023.8A Pending CN117466694A (zh) 2023-10-23 2023-10-23 一种构建季碳中心的方法

Country Status (1)

Country Link
CN (1) CN117466694A (zh)

Similar Documents

Publication Publication Date Title
CN111675662B (zh) 一种2-三氟甲基取代的喹唑啉酮化合物的制备方法
CN108276287B (zh) 一种可见光催化的4-氧代丙烯酸酯类衍生物的合成方法
CN113698325A (zh) 一种制备烷基磺酰氟的方法
CN112321553B (zh) 由芳基炔酸酯合成3位二氟甲基取代香豆素衍生物的方法
CN110028451B (zh) 一种全取代吡唑衍生物制备方法
CN114573512B (zh) 一种合成c2-二氟烷基苯并咪唑衍生物的方法
CN117466694A (zh) 一种构建季碳中心的方法
CN111004234A (zh) 一种2-苯基咪唑并[1,2-α]吡啶类化合物的C3位卤化方法
JP2022516863A (ja) スルホンアミド除草剤プロセス中間生成物の調製
CN113880781B (zh) 一种以葡萄糖为碳源合成3-三氟甲基取代的1,2,4-三氮唑化合物的方法
CN106146271B (zh) 一种由芳基磺酸酯制备二芳基甲酮的方法
CN106397377B (zh) 一种富电子五元杂环酸及其衍生物脱羧上氟的方法
CN110724094B (zh) 一种喹啉类化合物及其合成方法
CN111662290B (zh) 一种苯并吲哚嗪类化合物及其合成方法
CN104478799B (zh) 1,4-二烯丙基异喹啉的制备方法
CN108640914B (zh) 一种合成异吲哚[2,1-b]异喹啉-5,7-二酮类化合物的方法
CN107935913B (zh) 咔唑类化合物及其合成方法和应用
CN107721917B (zh) 一种多取代烟酸酯类化合物的绿色合成方法
CN108147989B (zh) 一种β-胺基酮衍生物及其合成方法
CN108794470B (zh) 一种6-肼基-1H-吡唑并[3,4-b]吡啶及其下游产品的合成方法
CN113072478B (zh) 一种铜催化下n-芳基吲哚的制备方法
CN113024604B (zh) 一种c3-烯基化的2-吡啶酮类衍生物的制备方法
Wu et al. CuLi2Cl4 catalysed cross-coupling strategy for the formal synthesis of the diterpenoid (+)-subersic acid from (–)-sclareol
CN111732508B (zh) 一种螺环化合物的合成方法
CN113200812B (zh) 1,3,5-三取代芳基化合物的合成方法

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