ɑ-碘代烯酰基二硫缩烯酮与炔类化合物的Sonogashira反应
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摘要
烯炔化合物是药物和天然产物的重要骨架,其合成方法一直受到有机合成化学家们的重视。近年来,Sonogashira反应一直是合成烯炔化合物的重要方法。本文以ɑ-碘代烯酰基二硫缩烯酮与端炔类化合物,考察了钯催化剂种类与用量、碱种类与用量、溶剂、底物结构等对偶联反应的影响,通过Sonogashira偶联反应,合成了一系列的ɑ-芳炔基烯酰基二硫缩烯酮类化合物,通过核磁共振、质谱分析对所得化合物进行了表征,并对该反应机理进行了探讨。
Eneyne compounds are paramount skeletons in pharmaceuticals and natural products,and great importance has been attached to its synthesis by organic synthetic chemist.Sonogashira reaction has been an important method to synthesize eneyne compounds.In this paper,ɑ-iodine alkenoyl ketene dithioacetals and terminal alkynes were used to synthesis a serials of ɑ-aryl alkynyl alkenoyl ketene dithioacetals compounds by the Sonogashira reaction.The influences of catalyst kinds and dosage,base kinds and dosage,solvent,and different substrates were investigated.The structure was confirmed by IR,~1H NMR,~(13)C NMR.Moreover,a mechanism for the reaction was proposed.
Eneyne compounds are paramount skeletons in pharmaceuticals and natural products,and great importance has been attached to its synthesis by organic synthetic chemist.Sonogashira reaction has been an important method to synthesize eneyne compounds.In this paper,ɑ-iodine alkenoyl ketene dithioacetals and terminal alkynes were used to synthesis a serials of ɑ-aryl alkynyl alkenoyl ketene dithioacetals compounds by the Sonogashira reaction.The influences of catalyst kinds and dosage,base kinds and dosage,solvent,and different substrates were investigated.The structure was confirmed by IR,~1H NMR,~(13)C NMR.Moreover,a mechanism for the reaction was proposed.
引文
[1]Diek H A,Heck F R.Palladium catalyzed synthesis of aryl,heterocyclic and vinylic acetylene derivatives[J].J Organomet Chem,1975,93:259-263.
[2]Cassar L.Synthesis of aryl-and vinyl-substituted acetylene derivatives by the use of nickel and palladium complexes[J].J Organomet Chem,1975,93:253-257.
[3]Sonogashira K,Tohda Y,Hagihara N.A convenient synthesis of acetylenes:catalytic substitutions of acetylenic hydrogen with bromoalkenes,iodoarenes and bromopyridines[J].Tetrahedron Lett,1975,16:4 467-4 470.
[4]王明明,王子潇,商明,等.过渡金属催化的 C-H 炔基化反应[J].有机化学,2015,35:570-577.
[5]王晔峰,邓维,刘磊,等.Sonogashira 反应研究的最新进展[J].有机化学,2005,25:8-24.
[6]王仙芳,唐星华,张波,等.有机高分子负载的 Sonogashira 反应的研究进展[J].化学研究与应用,2011,23(5).514-520.
[7]黄静,鲍涵,徐铭,等.2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛肟的合成[J].化学研究与应用,2018,30(11):1 886-1 891.
[8]Wang J X,Liu Z,Hu Y,et al.Microwave-assisted copper catalyzed coupling reaction of aryl halides with terminal alkynes[J].Synth Commun,2002,32:1 937-1 945.
[9]Bates C G,Saejueng P,Murphy J M,et al.Synthesis of 2-arylbenzo[b]furans via copper(I)-catalyzed coupling of o-iodophenols and aryl acetylenes[J].Org Lett,2002,4(26):4 727-4 729.
[10]Cacchi S,Fabrizi G,Parisi L.M.2-Aryl and 2-heteroaryl indoles from 1-alkynes and o-iodotrifluoroacetanilide through a domino copper-catalyzed coupling-cyclization process[J].Org Lett,2003,5(21):3 843-3 846.
[11]Ming W B,Liu X C,Wang M,et al.Tandem thien-and benzannulations of α-alkenoyl-α-alkynyl ketene dithioacetals with cyanoacetates:synthesis of functionalized benzo[b]thiophenes[J].Org Lett,2015,17:1 746-1 749.
[12]Han X D,Ren C Q,Fu J P,et al.An intramolecular cycloaddition approach to construct polysubstituted pyrrolidones from alkynyl carboxamides and PTSA[J].Synthesis,2017,49:4 703-4 710.
[13]Ren C Q,Di C H,Zhao Y L,et al.[3+2]Cycloadditions of α-acyl ketene dithioacetals with propargylamines:pyrrole synthesis in water[J].Tetrahedron Lett,2013,54:1 478-1 481.
[2]Cassar L.Synthesis of aryl-and vinyl-substituted acetylene derivatives by the use of nickel and palladium complexes[J].J Organomet Chem,1975,93:253-257.
[3]Sonogashira K,Tohda Y,Hagihara N.A convenient synthesis of acetylenes:catalytic substitutions of acetylenic hydrogen with bromoalkenes,iodoarenes and bromopyridines[J].Tetrahedron Lett,1975,16:4 467-4 470.
[4]王明明,王子潇,商明,等.过渡金属催化的 C-H 炔基化反应[J].有机化学,2015,35:570-577.
[5]王晔峰,邓维,刘磊,等.Sonogashira 反应研究的最新进展[J].有机化学,2005,25:8-24.
[6]王仙芳,唐星华,张波,等.有机高分子负载的 Sonogashira 反应的研究进展[J].化学研究与应用,2011,23(5).514-520.
[7]黄静,鲍涵,徐铭,等.2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛肟的合成[J].化学研究与应用,2018,30(11):1 886-1 891.
[8]Wang J X,Liu Z,Hu Y,et al.Microwave-assisted copper catalyzed coupling reaction of aryl halides with terminal alkynes[J].Synth Commun,2002,32:1 937-1 945.
[9]Bates C G,Saejueng P,Murphy J M,et al.Synthesis of 2-arylbenzo[b]furans via copper(I)-catalyzed coupling of o-iodophenols and aryl acetylenes[J].Org Lett,2002,4(26):4 727-4 729.
[10]Cacchi S,Fabrizi G,Parisi L.M.2-Aryl and 2-heteroaryl indoles from 1-alkynes and o-iodotrifluoroacetanilide through a domino copper-catalyzed coupling-cyclization process[J].Org Lett,2003,5(21):3 843-3 846.
[11]Ming W B,Liu X C,Wang M,et al.Tandem thien-and benzannulations of α-alkenoyl-α-alkynyl ketene dithioacetals with cyanoacetates:synthesis of functionalized benzo[b]thiophenes[J].Org Lett,2015,17:1 746-1 749.
[12]Han X D,Ren C Q,Fu J P,et al.An intramolecular cycloaddition approach to construct polysubstituted pyrrolidones from alkynyl carboxamides and PTSA[J].Synthesis,2017,49:4 703-4 710.
[13]Ren C Q,Di C H,Zhao Y L,et al.[3+2]Cycloadditions of α-acyl ketene dithioacetals with propargylamines:pyrrole synthesis in water[J].Tetrahedron Lett,2013,54:1 478-1 481.
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