过渡金属铑催化的环状亚胺与炔烃的[3+2]环合反应的研究
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摘要
在过渡金属铑催化作用下,3-苯基-2H-苯并[b][1,4]噁嗪类环状亚胺为底物与二苯基乙炔进行[3+2]环合反应,实现了五元碳环的构筑从而获得了多环状的茚基骨架的手性胺。考察了反应溶剂、添加剂种类、反应时间、反应温度及芳烃结构对反应的影响,确定了最佳的反应条件:0.24 mmol二苯基乙炔与0.2 mmol环状亚胺反应,在[Cp~*RhCl_2]_2(2.5 mol%)、醋酸铜(20 mol%)作用下,反应温度为50℃,时间为12 h。在此反应条件下,富电子的芳烃反应较好,缺电子的芳烃反应相对较差,富电子的炔类物质产率略低。
A rhodium-catalyzed [3+2] annulations reaction of 3-phenyl-2H-benzo[b][1,4]oxazine ring imine substrates and 1,2-disubstituted acetylene was realized and a five-membered carbon ring structure was successfully constructed to form a pericyclic indenyl amine. The effects of solvent, additive, reaction time, reaction temperature and the structure of arene on the reaction were investigated. The optimal reaction conditions were as follows: 0.24 mmol of diphenylacetylene, 0.2 mmol of cyclic imine in the presence of [Cp*RhCl_2]_2(2.5 mol%) and copper acetate(20 mol%) at 50 ℃ for 12 h. Under these conditions, the electron rich arenes react more effectively than the electron deficient arenes, and the electron rich acetylenes yields slightly lower.
A rhodium-catalyzed [3+2] annulations reaction of 3-phenyl-2H-benzo[b][1,4]oxazine ring imine substrates and 1,2-disubstituted acetylene was realized and a five-membered carbon ring structure was successfully constructed to form a pericyclic indenyl amine. The effects of solvent, additive, reaction time, reaction temperature and the structure of arene on the reaction were investigated. The optimal reaction conditions were as follows: 0.24 mmol of diphenylacetylene, 0.2 mmol of cyclic imine in the presence of [Cp*RhCl_2]_2(2.5 mol%) and copper acetate(20 mol%) at 50 ℃ for 12 h. Under these conditions, the electron rich arenes react more effectively than the electron deficient arenes, and the electron rich acetylenes yields slightly lower.
引文
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[4] Colby D A,Bergman R G,Ellman J A.Stereoselective Alkylation of α,β-Unsaturated Imines via C—H Bond Activation [J].J Am Chem Soc,2006,128(17):5 604-5 605.
[5] Colby D A,Bergman R G,Ellman J A.Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C—H Activation [J].J Am Chem Soc,2008,130(11):3 645-3 651.
[6] Fukutani T,Umeda N,Hirano K,et al.Rhodium-catalyzed Oxidative Coupling of Aromatic Imines with Internal Alkynes via Regioselective C—H Bond Cleavage [J],Chem Commun,2009,34:5 141-5 143.
[7] Guimond N,Fagnou K.Isoquinoline Synthesis via Rhodium-catalyzed Oxidative Cross-coupling/Cyclization of Aryl Aldimines and Alkynes [J].J Am Chem Soc,2009,131(34):12 050-12 051.
[8] Stuart D R,Alsabeh P,Kuhn M,et al.Rhodium(Ⅲ)-catalyzed Arene and Alkene C—H Bond Functionalization Leading to Indoles and Pyrroles [J].J Am Chem Soc,2010,132:18 326-18 339.
[9] Tran D N,Cramer N.Enantioselective Rhodium(I)-Catalyzed [3+2] Annulations of Aromatic Ketimines Induced by Directed C—H Activations [J].Angew Chem Int Ed,2011,50(47):11 098-11 102.
[10] Ye B,Cramer N.Chiral Cyclopentadienyl Ligands as Stereocontrolling Element in Asymmetric C—H Functionalization [J].Science,2012,338:504-506.
[11] Chen Y,Wang F,Zhen W,et al.Rhodium(Ⅲ)-catalyzed Annulation of Azomethine Ylides with Alkynes via C—H Activation [J].Adv Synth Catal,2013,355(2-3):353-359.
[12] Sharma S,Oh Y,Mishra N K,et al.Rhodium-catalyzed [3+2] Annulation of Cyclic N-Acyl Ketimines with Activated Olefins:Anticancer Activity of Spiroisoindolinones [J].J Organ Chem,2017,82(7):3 359-3 367.
[13] Zhang Y.A Novel Reduction of o-Nitrophenoxy Compounds Promoted by Low-valent Titanium:An Access to 2H-1,4-Benzoxazine Derivatives [J].J Chem Res Synopses,2000(8):388-389.
[14] Jiang Y,Liu L X,Zhang X M,et al.Lewis Base Organocatalyzed Enantioselective Hydrosilylation of 1,4-Benzoxazines [J].Synlett,2012,23:179.
[15] Joseé L N,Anton V F.[Ir(P-OP)]-Catalyzed Asymmetric Hydrogenation of Diversely Substituted C=N-Containing Heterocycles [J].Org Lett,2013,15(8):2 066-2 069.
[16] Zhang Y,Zhao R,Bao R L.Highly Enantioselective Spinol-derived Phosphoric Acid Catalyzed Transfer Hydrogenation of Diverse C:N-Containing HeterocyclesYiliang Zhang [J].Eur J Org Chem,2015,15:3 344-3 351.
[17] Lapointe D,Fagnou K.Overview of the Mechanistic Work on the Concerted Metallation-deprotonation Pathway [J].Chem Lett,2010,39(11):1 118-1 126.
[18] Li B J,Wang H Y,Zhu Q L,et al.Rhodium/Copper-catalyzed Annulation of Benzimides with Internal Alkynes:Indenone Synthesis Through Sequential C—H and C—N Cleavage [J].Angew Chem Int Ed Engl,2012,51(16):3 948-3 952.