CN114907257B - 一种可见光诱导催化非活化烯烃卤代吡啶化的方法 - Google Patents

一种可见光诱导催化非活化烯烃卤代吡啶化的方法 Download PDF

Info

Publication number
CN114907257B
CN114907257B CN202110168433.8A CN202110168433A CN114907257B CN 114907257 B CN114907257 B CN 114907257B CN 202110168433 A CN202110168433 A CN 202110168433A CN 114907257 B CN114907257 B CN 114907257B
Authority
CN
China
Prior art keywords
olefin
pyridine
reaction
visible light
photocatalyst
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
CN202110168433.8A
Other languages
English (en)
Other versions
CN114907257A (zh
Inventor
陈庆安
郭诗宇
杨帆
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.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
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 Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN202110168433.8A priority Critical patent/CN114907257B/zh
Publication of CN114907257A publication Critical patent/CN114907257A/zh
Application granted granted Critical
Publication of CN114907257B publication Critical patent/CN114907257B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
    • 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/127—Preparation from compounds containing pyridine rings
    • 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • 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
    • 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
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/42—Radicals substituted by singly-bound nitrogen atoms having hetero atoms attached to the substituent nitrogen atom
    • 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)
  • Pyridine Compounds (AREA)

Abstract

本发明涉及卤代吡啶及其衍生物与非活化烯烃交叉偶联的方法。具体为，以简单卤代吡啶和非活化烯烃为起始原料，在可见光/光催化剂/添加剂/反应溶剂促进条件下，可以在烯烃双键两端同时引入卤素和吡啶基团。本发明有以下优点，原料简单易得，合成简单，环境友好，条件温和，原子和步骤经济性高，底物适用范围广泛且易放大，该类化合物是一类重要的吡啶基杂环化合物，且具有活性碳卤键活性位点，是重要的结构骨架和合成前体。

Description

一种可见光诱导催化非活化烯烃卤代吡啶化的方法
技术领域
本发明属于有机化合物合成方法技术领域，涉及一种卤代吡啶及其衍生物与非活化烯烃交叉偶联的方法。具体为，以卤代吡啶和烯烃为原料，在可见光/光催化剂/添加剂/反应溶剂促进下，可以在烯烃双键高效地引入卤素和吡啶基团。本发明有以下优点，原料卤代吡啶和烯烃来源广泛商业易得，具有较高的反应原子经济性和步骤经济性，直接一步就可高效的引入卤素基团和吡啶基团；温和可见光室温反应条件，具有广泛的底物适用范围易放大，产物可作为活性合成前体进一步转化。
背景技术
从简单底物出发高效构建复杂化合物分子一直是有机化学的重要主题。烯烃是一类来源丰富、廉价易得的重要有机合成原料，烯烃的催化官能化反应受到有机化学家的广泛关注。经典的Heck偶联反应使芳基卤代物和烯烃在金属钯催化下可以快速得到烯烃的芳基化产物。此外，通过引入外部氢源可以发生芳基卤代物与烯烃的氢芳基化反应来获得各种还原性的Heck偶联产物。尽管它们具有广泛的适用性，但是这两个过程都不可避免的涉及卤原子的消除使卤原子浪费。鉴于碳—卤键也是一类非常重要的结构单元，因此如何对烯烃双键同时构建碳—碳键和碳—卤键实现烯烃的卤代芳基化，而无需浪费任何原子吸引了化学家们的思考。
通过文献检索发现，2011年，Lautens等报道了金属钯催化的分子内烯烃的芳碘化反应，钯催化剂与大膦配体的使用是控制反应活性和选择性的关键。在随后的几年中，Lautens、Tong、Zhang等也相继报道了钯/镍催化的烯烃的芳碘化反应，但底物仅限特定的分子内烯烃，且要求烷基钯/镍卤代物中间体不存在synβ-H原子(式1)。因此，探寻底物适用范围更广的分子间烯烃卤代芳基化反应是一个挑战。
吡啶是一类非常重要的杂芳环结构单元，它在配体骨架、天然产物、药物活性分子中无处不在，例如，用于降低低密度脂蛋白胆固醇水平Cerivastatin、雄性激素合成抑制剂Abiraterone acetate、具用于治疗严重COPD患者支气管炎相关咳嗽和黏液过多症状Roflumilast(式2)。近年来，光促进氧化还原是催化烯烃官能化反应的先进技术。因此，探索高效、温和、原子经济性强、底物适用范围广的光催化体系实现烯烃的卤代吡啶化反应具有重要意义。
卤代吡啶和烯烃是常见的工业大宗化学品，廉价易得。本专利开发出了一种可见光诱导催化烯烃卤代吡啶化的反应，可以在烯烃双键两端同时引入卤素和吡啶基团。
发明内容
本发明目的在于以简单化学品非活化烯烃和卤代吡啶为原料，发展了一种可见光/光催化剂/添加剂/反应溶剂体系，可以在烯烃双键位高效地引入卤素基团和吡啶基团。
本发明是通过以下技术方案实现的：
卤代吡啶1和非活化烯烃2(端烯、链状内烯或环状内烯)在可见光、光催化剂、添加剂以及反应溶剂作用下，可以在烯烃双键两端同时引入卤素和吡啶基团(或者取代的吡啶)，反应式如下所示：
具体操作步骤如下：
在氩气或氮气气氛下，加入光催化剂，然后加入一定量的溶剂溶解，再依次加入卤代吡啶1、烯烃2、添加剂，在可见光照射和室温下反应，薄层层析点板监测反应体系，反应结束后，加入适量碱调节体系为弱碱性，旋干溶剂，柱层析(流动相：石油醚/乙酸乙酯＝15/1)得到目标产物3。
本发明有以下优点：
本发明有以下优点，原料简单易得，合成简单，环境友好，条件温和，原子和步骤经济性高，底物适用范围广泛且易放大，该类化合物是一类重要的吡啶基杂环化合物，且具有活性碳卤键活性位点，是重要的结构骨架和合成前体。
具体实施方式
下面将以具体的实施例来对本发明加以说明，但本发明的保护范围不局限于这些实例。
可见光诱导催化卤代吡啶和烯烃的反应
在4.0mL小瓶中，加入光催化剂(相对于1.0equiv.2-溴-6-甲基吡啶1a用量的1mol％)，用2.5mL溶剂溶解，再依次加入2-溴-6-甲基吡啶1a(0.5mmol,57μL,1.0equiv.)、1-己烯2a(1.5mmol,186μL)、添加剂(0.5mmol)，氮气环境保护密封，然后用最大波长456nm、40W的蓝光照射，反应过程中采用薄层层析点板监测反应体系，在室温反应16h，结束后加入0.2mL三乙胺(此时体系PH＝7.2)，再加入1.0mmol均三甲氧基苯作为内标，1HNMR检测目标产物3a收率。
表1.光催化剂、添加剂、溶剂等因素对反应的影响
由表1结果可以看出，2-溴-6-甲基吡啶1a与1-己烯2a摩尔比1:3时，用最大波长456nm、40W的蓝光照射，在室温反应，以(4,4′-二叔丁基-2,2′-联吡啶)双[(2-吡啶基)苯基]铱(六氟磷酸)盐为光催化剂，三氟乙酸为添加剂，三氟乙醇为反应溶剂时，以88％收率得到目标产物(实施例1)。当光催化剂不是(4,4′-二叔丁基-2,2′-联吡啶)双[(2-吡啶基)苯基]铱(六氟磷酸)盐时，如：(4,4′-二叔丁基-2,2′-联吡啶)双[(4-氟-2-吡啶基)苯基]铱(六氟磷酸)盐、二[2-(2,4-二氟苯基)-5-三氟甲基吡啶][2-2′-联(4-叔丁基吡啶)]铱(六氟磷酸)盐等，目标产物收率降低(实施例1-7)。当溶剂不是三氟乙醇时，如：六氟异丙醇、乙醇等，目标产物收率降低(实施例8-17)。当更换添加剂为特戊酸，乙酸，苯甲酸，二苯氧基磷酸，苯磺酸，盐酸时，收率为0％或降低(实施例19-24)。因此，优选光催化剂是(4,4′-二叔丁基-2,2′-联吡啶)双[(2-吡啶基)苯基]铱(六氟磷酸)盐，添加剂是三氟乙酸，溶剂是三氟乙醇，蓝光最大波长456nm、40W，室温，反应时间16h。
2.底物类型
在手套箱，向4.0mL小瓶中，加入Ir(ppy)2(dtbbpy)PF6(4.6mg,1mol％),用2.0mLTFE溶解，再依次加入卤代吡啶1(0.5mmol,1.0equiv.)、烯烃2(3.0equiv)、TFA(74.6μL,1.0equiv)，用最大波长456nm、40W蓝光照射，反应过程中采用薄层层析点板监测反应体系，在室温反应16h，反应结束后，加入饱和碳酸氢钠溶液调节体系为PH＝7.5，乙酸乙酯萃取，旋干溶剂，柱层析分离，流动相为石油醚/乙酸乙酯15:1(v/v)，得到目标产物3。
2-(2-Bromohexyl)-6-methylpyridine(3aa):Colorlessoil,111.4mg,87％yield.1H NMR(400MHz,Chloroform-d)δ7.51(t,J＝7.7Hz,1H),7.01(t,J＝7.9Hz,2H),4.52–4.44(m,1H),3.30(dd,J＝14.2,5.2Hz,1H),3.22(dd,J＝14.2,8.9Hz,1H),2.53(s,3H),1.96–1.81(m,2H),1.66–1.55(m,1H),1.52–1.39(m,1H),1.37–1.26(m,2H),0.91(t,J＝7.3Hz,3H).13C NMR(100MHz,Chloroform-d)δ158.22,157.95,136.62,121.48,121.13,57.20,48.03,38.75,29.81,24.65,22.26,14.11.HRMS calculated forC12H19BrN[M+H]+256.0695,found 256.0696.
2-(2-Bromooctyl)-6-methylpyridine(3ab):Colorlessoil,126.5mg,89％yield.1H NMR(400 MHz,Chloroform-d)δ7.49(t,J＝7.7 Hz,1H),7.00(t,J＝7.9Hz,2H),4.53–4.43(m,1H),3.29(dd,J＝14.2,5.3 Hz,1H),3.21(dd,J＝14.2,8.9 Hz,1H),2.53(s,3H),1.95–1.79(m,2H),1.69–1.55(m,1H),1.51–1.40(m,1H),1.33–1.24(m,6H),0.87(t,J＝6.8 Hz,3H).13C NMR(100 MHz,Chloroform-d)δ158.20,157.95,136.54,121.42,121.07,57.18,48.03,39.01,31.78,28.77,27.58,24.65,22.69,14.18.HRMScalculated for C14H23BrN[M+H]+284.1008,found 284.1010.
5-Bromo-6-(6-methylpyridin-2-yl)hexan-1-ol(3ac):Colorless oil,113.0mg,83％yield.1H NMR(400 MHz,Chloroform-d)δ7.51(t,J＝7.6 Hz,1H),7.00(t,J＝8.2Hz,2H),4.53–4.42(m,1H),3.64(t,J＝5.9 Hz,2H),3.30(dd,J＝14.1,5.3 Hz,1H),3.22(dd,J＝14.1,8.7 Hz,1H),2.52(s,3H),2.14(brs,1H),1.99–1.83(m,2H),1.77–1.66(m,1H),1.65–1.51(m,3H).13C NMR(100 MHz,Chloroform-d)δ158.21,157.75,136.72,121.59,121.23,62.46,56.64,47.68,38.41,32.04,24.52,23.79.HRMS calculated forC12H19BrNO[M+H]+272.0645,found 272.0647.
3-Bromo-2-methyl-4-(6-methylpyridin-2-yl)butan-2-ol(3ad):Colorless oil,92.9 mg,72％yield.1H NMR(400 MHz,Chloroform-d)δ7.53(t,J＝7.7 Hz,1H),7.02(t,J＝8.0 Hz,2H),4.52(dd,J＝9.0,3.9 Hz,1H),3.76(brs,1H),3.53(dd,J＝14.9,3.9 Hz,1H),3.26(dd,J＝14.9,9.0 Hz,1H),2.53(s,3H),1.48(s,3H),1.45(s,3H).13CNMR(100 MHz,Chloroform-d)δ157.87,157.82,137.02,121.59,121.51,72.61,66.50,42.48,27.76,26.81,24.31.HRMS calculated for C11H17BrNO[M+H]+258.0488,found258.0490.
2-(2-Bromo-2-cyclohexylethyl)-6-methylpyridine(3ae):Colorlessoil,118.5 mg,84％yield.1H NMR(400 MHz,Chloroform-d)δ7.49(t,J＝7.7Hz,1H),6.99(t,J＝8.4 Hz,2H),4.47(dt,J＝10.0,3.9 Hz,1H),3.30(dd,J＝14.3,4.3Hz,1H),3.19(dd,J＝14.3,10.0 Hz,1H),2.53(s,3H),1.94–1.87(m,1H),1.86–1.73(m,4H),1.70–1.64(m,1H),1.62–1.53(m,1H),1.43–1.33(m,1H),1.28–1.21(m,2H),1.21–1.10(m,1H).13CNMR(100MHz,Chloroform-d)δ158.33,158.20,136.54,121.38,121.07,64.21,45.10,44.45,31.54,28.74,26.42,26.31,26.16,24.66.HRMS calculated for C14H21BrN[M+H]+282.0852,found 282.0853.
应用例1：
在氮气保护条件下，向反应瓶中添加合成的产物3aa(0.5mmol，1.0equiv)，NaN3(1.0mmol，2.0equiv)，溶解在DMF中(2mL)，升温至80℃反应18h后,柱层析分离纯化，得到目标产物4，化合物结构经过核磁(氢谱，碳谱，高分辨)确认。
应用例2
在氮气保护条件下，向反应瓶中添加合成的产物3aa(0.5mmol，1.0equiv)，DBU(1.0mmol，2.0equiv)，溶解在Toluene中(2mL)，升温至110℃反应12h后,柱层析分离纯化，得到目标产物5，化合物结构经过核磁(氢谱，碳谱，高分辨)确认。

Claims (8)

1.一种可见光诱导催化烯烃卤代吡啶化的方法，其特征在于：
卤代吡啶和烯烃在可见光、光催化剂、添加剂以及反应溶剂作用下，在烯烃双键两端同时引入卤素、以及吡啶基团或者取代的吡啶；
所述光催化剂为下述中的一种或二种以上：(4,4'-二叔丁基-2,2'-联吡啶)双[(2-吡啶基)苯基]铱(六氟磷酸)盐、[2,2'-联(4-叔丁基吡啶)]双[2-(4-氟苯基)吡啶]铱(六氟磷酸)盐；
所用的添加剂为下述中的一种或二种以上：三氟乙酸、二苯氧基磷酸、苯磺酸；
所用溶剂为三氟乙醇、六氟异丙醇中的一种或二种以上；
所述烯烃为端烯、链状内烯或环状内烯中的一种或二种以上；
反应式如下所示中的一种或二种以上：
具体操作步骤如下：
在氩气和/或氮气气氛下，加入光催化剂，加入溶剂溶解，再加入卤代吡啶1、烯烃2、添加剂，在可见光照射下反应，得到目标产物3；
反应物卤代吡啶1上的取代基R是氢、甲基、甲氧基中的一种二种以上；其个数为1-4个；
反应物卤代吡啶上的卤代基X是氯、溴、碘中的一种或二种以上，取代基X在吡啶的2位、3位、4位、5位或6位；其个数为1-4个；
烯烃2上的取代基R1、R2和R3是氢、C2-C20的链状烷基、C1-C8环烷基、C2-C20的烷基醇、C1-C20烷基醚、C2-C20的烷基卤中的一种二种以上，R1、R2和R3不可同时为氢；
环状内烯中n = 1 – 4；
所述可见光的波长范围是390 nm – 480 nm；
所述可见光的功率为5 W – 50 W；
反应温度在10-60 ºC之间；
反应时间在1-35 h之间；
卤代吡啶于溶剂中的浓度范围0.01-1.00 mol/L；
烯烃用量是卤代吡啶摩尔量的1.0-10.0倍之间。
2.根据权利要求1所述的方法，其特征在于：
可见光波长范围为440 - 460 nm；
反应温度在20-30 ºC之间；
反应时间在15-25 h之间；
卤代吡啶于溶剂中的浓度范围0.05-1.00 mol/L；
烯烃用量是卤代吡啶摩尔量的2.0-5.0倍之间。
3.根据权利要求1或2所述的方法，其特征在于：
反应过程中采用薄层层析点板监测反应体系，反应结束后，加入饱和碳酸氢钠水溶液和/或三乙胺适量调节体系为PH=7-8，旋干溶剂，柱层析分离得到目标产物3，所述柱层析流动相为石油醚/乙酸乙酯 =5:1—20:1，v/v。
4.根据权利要求1或2所述的方法，其特征在于：
所述光催化剂为 (4,4'-二叔丁基-2,2'-联吡啶)双[(2-吡啶基)苯基]铱(III)六氟磷酸盐。
5.根据权利要求1或2所述的方法，其特征在于：
光催化剂为卤代吡啶的摩尔量的0.05-5.00 mol%。
6.根据权利要求1或2所述的方法，其特征在于：
添加剂与卤代吡啶的摩尔比为0.5-5.0。
7.根据权利要求5所述的方法，其特征在于：光催化剂为卤代吡啶的摩尔量的0.5- 2.0mol%。
8.根据权利要求6所述的方法，其特征在于：
添加剂与卤代吡啶的摩尔比为1.0-2.0。
CN202110168433.8A 2021-02-07 2021-02-07 一种可见光诱导催化非活化烯烃卤代吡啶化的方法 Active CN114907257B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110168433.8A CN114907257B (zh) 2021-02-07 2021-02-07 一种可见光诱导催化非活化烯烃卤代吡啶化的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110168433.8A CN114907257B (zh) 2021-02-07 2021-02-07 一种可见光诱导催化非活化烯烃卤代吡啶化的方法

Publications (2)

Publication Number Publication Date
CN114907257A CN114907257A (zh) 2022-08-16
CN114907257B true CN114907257B (zh) 2023-11-24

Family

ID=82760872

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110168433.8A Active CN114907257B (zh) 2021-02-07 2021-02-07 一种可见光诱导催化非活化烯烃卤代吡啶化的方法

Country Status (1)

Country Link
CN (1) CN114907257B (zh)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110734389A (zh) * 2019-09-29 2020-01-31 台州学院 一种二烷基砜类化合物的制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110734389A (zh) * 2019-09-29 2020-01-31 台州学院 一种二烷基砜类化合物的制备方法

Also Published As

Publication number Publication date
CN114907257A (zh) 2022-08-16

Similar Documents

Publication Publication Date Title
EP3245191B1 (en) Quinolines and process for the preparation thereof
CN108864147B (zh) 一种八元氮氧杂环螺吲哚酮化合物及制备方法
CN114907257B (zh) 一种可见光诱导催化非活化烯烃卤代吡啶化的方法
Jiao et al. 1, 2, 3-Triazol-5-ylidene bearing a pyridine auxiliary based bidentate PEPPSI type palladium (II) complex: Synthesis, structure, and application in the direct arylation of pyridine N-oxide
CN111484436A (zh) 一种在吲哚c3位引入异戊烯基的方法
CN111484437A (zh) 一种在吲哚c3位引入叔异戊烯基的方法
Tjosaas et al. Palladium complexes of N-aryl-2-pyridylamines
JP2017132738A (ja) ビピリジル化合物の製造方法
CN105001156A (zh) 一种喹啉衍生物的三组分反应体系合成方法
CN109438451A (zh) 一级胺导向构建6-(2-溴苯基)吲哚并[1,2-a]喹喔啉的方法
CN109503603A (zh) 一级胺导向构建6-(4-正丁基苯基)吲哚并[1,2-a]喹喔啉的方法
CN113024604B (zh) 一种c3-烯基化的2-吡啶酮类衍生物的制备方法
CN113173921B (zh) 一种6-噻吩基吡啶酮化合物及其合成方法
Yi et al. Trifluoromethylthiolation of Aromatic and Heteroaromatic Compounds
CN114315724A (zh) 一种钯催化共轭二烯氢胺化的方法
Antoniou et al. LED-induced Ru-photoredox Pd-catalyzed C–H arylation of (6-phenylpyridin-2-yl) pyrimidines and heteroaryl counterparts
CN114315725A (zh) 一种在吲唑n2位引入叔异戊烯基的方法
CN109575034A (zh) 一级胺导向构建6-苯基吲哚并[1,2-a]喹喔啉的方法
Feng et al. N, N-Dimethylformamide (DMF)-Promoted SpecificN-Alkylation of Hydroxyl N-Heterocycles with Organohalides: A Direct and Efficient Method for Synthesis of Pyridone Derivatives
CN114621148A (zh) 一种钯催化吲唑n1位引入二甲基烯丙基(4,3-加成）的方法
CN109627249A (zh) 一级胺导向构建6-(萘-1-基)吲哚并[1,2-a]喹喔啉的方法
CN109608467A (zh) 一级胺导向构建8-氯-6-苯基吲哚并[1,2-a]喹喔啉的方法
CN109503598A (zh) 一级胺导向构建6-(4-氯苯基)吲哚并[1,2-a]喹喔啉的方法
CN109503595A (zh) 一级胺导向构建10-甲氧基-6-苯基吲哚并[1,2-a]喹喔啉的方法
CN109627247A (zh) 一级胺导向构建8-苄氧基-6-苯基吲哚并[1,2-a]喹喔啉的方法

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
GR01 Patent grant
GR01 Patent grant