铜铁共催化烯烃串联加成/环化合成异喹啉二酮

doi:10.3969/j.cnki.jdxb.2018.04.013

吉首大学学报（自然科学版）

铜铁共催化烯烃串联加成/环化合成异喹啉二酮

夏绿露，王良能，李增增，李荣杰，盛回香，吴亚琴，李培，李玲，唐石

(化学国家级实验教学示范中心，湖南吉首 416000)

出版日期:2018-11-25 发布日期:2018-12-07
通讯作者: 唐石(1979—)，男，湖南衡阳人，吉首大学化学与化工学院教授，博士，硕士生导师，E-mail:shitang@126.com.
基金资助:
国家自然基金资助资助项目(21662013)；湖南省自然基金资助项目（2018JJ1020）；吉首大学大学生科研项目（JDX16002）；吉首大学大学生研究性学习与创新性实验计划项目

Cu/Fe Co-Catalyzed Cascade Addition/Cyclization of Alkenes Toward Isoquinolinediones

XIA Lülu,WANG Liangneng,LI Zengzeng,SHENG Huixiang,TANG Shi

(National Demonstration Center for Experimental Chemistry Education,Jishou University,Jishou 416000,Hunan China)

Online:2018-11-25 Published:2018-12-07

摘要/Abstract

摘要：

发展了一种铜/铁协同催化的N-烯丙酰基苯甲酰胺串联加成/环化/偶联合成叔烷基化异喹啉二酮的反应.在廉价金属Cu/Fe协同催化作用下，烷基偶氮试剂介导N-丙烯酰基-N-烷基氯代苯甲酰胺发生串联加成/环化，区域选择性地切断C—Cl键而发生进一步交叉偶联，以41%~78%的产率合成了一系列远端双重α-官能团化叔烷基取代的异喹啉二酮骨架.该反应首次利用卤代苯甲酰胺去芳构化而形成的超共轭自由基为偶联体与偶氮试剂发生交叉偶联，选择性地在碳—卤键位置构建碳（叔）—碳键.此偶联策略将为深入拓展叔烷基-芳基交叉偶联提供新的思路.

关键词： 异喹啉二酮；自由基偶联；铜/铁共催化；烷基偶氮试剂, 串联反应

Abstract:

A Cu/Fe-cocatalyzed cascade addition/cyclizaion/cross-coupling of N-methacryloyl halobenzamides with azo reagents toward dual tert-alkylating isoquinolinediones was developed.Under the synergistic CuI/Fe catalysis,alkyl azo reagent mediated a cascade addition/cyclization of N-alkyl-N-methacryloyl halobenzamides,followed by further radical cross-coupling via the cleavage of C—Cl bond with site selectivity,leading to a series of dual tert-alkylating isoquinolinediones in 41%~78% yields.The reaction realized the radical cross-coupling of azo reagent with hyper-conjugated free radicals arising from a prior dearomatzation of methacryloyl halobenzamides and constructed the carbon (tertiary) -carbon bond at the position of C—Cl bond,thereby providing a new idea exploring the tertiary alkyl-aryl cross-coupling reactions.

Key words: isoquinolinediones, radical cross-coupling, synergistic Cu/Fe catalysis, alkyl azo reagent, tandem reaction

夏绿露，王良能，李增增，李荣杰，盛回香，吴亚琴，李培，李玲，唐石. 铜铁共催化烯烃串联加成/环化合成异喹啉二酮[J]. 吉首大学学报（自然科学版）, DOI: 10.3969/j.cnki.jdxb.2018.04.013.

XIA Lülu,WANG Liangneng,LI Zengzeng,SHENG Huixiang,TANG Shi . Cu/Fe Co-Catalyzed Cascade Addition/Cyclization of Alkenes Toward Isoquinolinediones[J]. Journal of Jishou University（Natural Sciences Edition), DOI: 10.3969/j.cnki.jdxb.2018.04.013.

参考文献

[1] ZHANG E,FAN C A,TU Y Q,et al.Organocatalytic Asymmetric Vinylogous α-Ketol Rearrangement:Enantioselective Construction of Chiral All-Carbon Quaternary Stereocenters in Spirocyclic Diketones via Semipinacol-Type 1,2-Carbon Migration[J].J Am Chem Soc,2009,131(41):14 626-14 627.
[2] MLLER D S,UNTIEDT N L,DIESKAU A P,et al.Constructing Quaternary Stereogenic Centers Using Tertiary Organocuprates and Tertiary Radicals.Total Synthesis of Trans-Clerodane Natural Products[J].J Am Chem Soc,2015,137(2):660-663.
[3] HINTERMANN L,XIAO L,LABONNE A.A General and Selective Copper-Catalyzed Cross-Coupling of Tertiary Grignard Reagents with Azacyclic Electrophiles[J].Angew Chem Int Ed Engl,2008,47(43):8 246-8 250.
[4] LOHRE C,DRGE T,WANG C,et al.Nickel-Catalyzed Cross-Coupling of Aryl Bromides with Tertiary Grignard Reagents Utilizing Donor-Functionalized N-Heterocyclic Carbenes (NHCs)[J].Chem-Eur J,2011,17(22):6 052-6 055.
[5] ZHANG N,SAMANTA S R,ROSEN B M,et al.Single Electron Transfer in Radical Ion and Radical-Mediated Organic,Materials and Polymer Synthesis[J].Chem Rev,2014,114(11):5 848-5 958.
[6] JIN J,MACMILLAN D W.Alcohols as Alkylating Agents in Heteroarene C—H Functionalization[J].Nature,2015,525:87-90.
[7] LACKNER G L,QUASDORF K W,OVERMAN L E.Direct Construction of Quaternary Carbons from Tertiary Alcohols Via Photoredox-catalyzed Fragmentation of Tert-Alkyl N-Phthalimidoyl Oxalates[J].J Am Chem Soc,2013,135(41):15 342-15 345.
[8] ODERINDE M S,FRENETTE M,ROBBINS D W,et al.Photoredox Mediated Nickel Catalyzed Cross-Coupling of Thiols with Aryl and Heteroaryl Iodides Via Thiyl Radicals[J].J Am Chem Soc,2016,138(6):1 760-1 763.
[9] ZHOU D,LI Z H,LI J,et al.Copper-Catalysed Alkylarylation of Activated Alkenes Using AIBN and Beyond:An Access to Cyano-Containing Oxindoles[J].European Journal of Organic Chemistry,2015(7):1 606-1 612.
[10] 张倩，王琼，邓佑林，等.光催化烯烃加成／环化合成含氟异喹啉-1，3-二酮[J].吉首大学学报（自然科学版），2017,38(3):69-75.
[11] KONG W,CASIMIRO M,FUENTES N,et al.Metal-Free Aryltrifluoromethylation of Activated Alkenes[J].Angew Chem Int Ed Engl,2013,52(49):13 086-13 090.

铜铁共催化烯烃串联加成/环化合成异喹啉二酮

Cu/Fe Co-Catalyzed Cascade Addition/Cyclization of Alkenes Toward Isoquinolinediones

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