钯催化烯基苯胺与重氮化合物的[3+2]环化反应
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摘要
二氢呋喃骨架化合物作为一类重要的有机合成中间体及药物分子构筑单元,广泛应用于有机合成与药物化学等领域.在醋酸钯催化作用下,以邻氨基苯乙烯为原料,重氮羰基化合物为3原子合成片段进行偶联转化,反应能够以51%～69%的产率合成七种含有季碳中心的新型二氢呋喃衍生物,并通过核磁共振氢谱、核磁共振碳谱、高分辨质谱、熔点等分析手段对产物进行了表征.该方法简洁高效,具有良好的官能团兼容性,为二氢呋喃类杂环化合物的合成提供了一条新途径,也探索拓宽了重氮羰基化合物的[n+3]环化反应.
As a kind of important organic synthesis intermediates and drug molecular building blocks,dihydrofuran skeleton compounds are widely used in organic synthesis and pharmaceutical chemistry.In this paper,under the catalysis of palladium acetate,o-aminostyrene is used as raw material,and diazocarbonyl is a 3-atom synthesis fragment for coupling conversion.The reaction can synthesize seven novel dihydrofuran derivatives containing quaternary carbon centers in 51%～69% yields,and the corresponding desired products were characterized by ~1H NMR,~(13)C NMR,HRMS,melting point and other analytical means.The method is simple and efficient and has good functional group compatibility,which provides a new way for the synthesis of dihydrofuran heterocyclic compounds.The [n+3] annulation reaction diazocarbonyl compounds that can participate in cyclization as a 3-atom synthesizer have also been developed.
As a kind of important organic synthesis intermediates and drug molecular building blocks,dihydrofuran skeleton compounds are widely used in organic synthesis and pharmaceutical chemistry.In this paper,under the catalysis of palladium acetate,o-aminostyrene is used as raw material,and diazocarbonyl is a 3-atom synthesis fragment for coupling conversion.The reaction can synthesize seven novel dihydrofuran derivatives containing quaternary carbon centers in 51%～69% yields,and the corresponding desired products were characterized by ~1H NMR,~(13)C NMR,HRMS,melting point and other analytical means.The method is simple and efficient and has good functional group compatibility,which provides a new way for the synthesis of dihydrofuran heterocyclic compounds.The [n+3] annulation reaction diazocarbonyl compounds that can participate in cyclization as a 3-atom synthesizer have also been developed.
引文
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[5] 俞寿云,程远征.烯烃和2-溴-1,3-二羰基化合物光氧化还原法合成多取代二氢呋喃[J].中国科技论文,2016,11(18):2 047-2 049.
[6] Alemán J,Jarava B C,Esteban F,et al.Asymmetric synthesis of trans-dihydroarylfurans in a Friedel-Crafts/substitution domino reaction under squaramide catal-ysis[J].Chem.Commun,2013,49:2 001-2 003.
[7] Feng J H,Lin L L,Yu K R,et al.Cover picture:Rhodium nanoflowers stabilized by a nitrogen-rich PEG-Tagged substrate as recyclable catalyst for the stereoselective hydrosilylation of internal alkynes[J].Synth.Catal,2015,357(1):1-7.
[8] Miao C B,Liu R,Sun Y F,et al.Base-controlled selective construction of polysubstituted dihydrofuran and furan derivatives through an I2-mediated cyclization[J].Tetrahedron Letters,2017,58(6):541-545.
[9] 鲁鸿,刘金宇,李红玉,等.氮杂环卡宾与过渡金属共催化反应研究进展[J].化学学报,2018,76(11):831-837.
[10] 刘睿.过渡金属催化构建季碳中心和羰基化反应[D].苏州:苏州大学,2017.
[11] 罗高雅,周青,施攀.铑催化的重氮化合物与吲哚的环加成反应[J].广东化工,2018,45(10):24-25.
[12] 卜秀斌.重氮化合物参与过渡金属催化的异腈串联反应研究[D].长春:东北师范大学,2018.
[13] Ding Q P,Wang C,Zheng Q,et al.An efficient route to quinoline-2-carboxylates via a rhodium-catalyzed oxidative [5+1] annulation of 2-vinylanilines with α-diazocarbonyl compounds[J].Tetrahedron,2018,74:348-353.
[14] Mandal S,Sakhuja R,Karishma P,et al.Additive-driven Rhodium-catalyzed [4+1]/[4+2] annulations of N-arylphthalazine-1,4-dione with α-diazo carbonyl compounds[J].J.Org.Chem,2018,83:11 661-11 673.
[15] Hu X P,Tong J,Li K,et al.Decarboxylation-promoted Pd-catalyzed asymmetric propargylic [3+2] annulation for the enantioselective construction of a quaternary stereocenter in 2,3-dihydrofurans[J].Org.Biomol.Chem,2018,16(5):742-749.
[16] Zhao F,Li N,Gong L Z,et al.Enantioselective Aza-Ene-type reactions of enamides with gold carbenes generated from a-diazoesters[J].Angew.Chem.Int.Ed,2017,129(12):3 295-3 299.
[17] Zhang X L,Feng K X,Xia A B,et al.Asymmetric synthesis of 2,3-dihydrofurans via one-pot michael addition/I2-mediated cyclization[J].Eur.J.Org.Chem,2018,23:2 918-2 925.