An unusual nickel-copper-mediated alkyne homocoupling reaction for the active-template synthesis of [2]rotaxanes
作者： James D. Crowley , Stephen M. Goldup , Nicholas D. Gowans , David A. Leigh , Vicki E. Ronaldson
DOI: 10.1021/JA101121J
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摘要: We report on an unusual Ni-/Cu-mediated alkyne homocoupling reaction, directed through the cavity of a bidentate macrocyclic ligand by chelated metal ions to furnish [2]rotaxanes in excellent (up 95%) yields. This is first active template reaction employ octahedral coordination geometry ion, Ni(II), and study provides some interesting mechanistic insights into mixed bimetallic mechanism. The mixed-metal catalyst system was discovered serendipitously when Cu(I) added Ni(II)-catalyzed attempt facilitate chloride−acetylide exchange. role is, fact, quite different from that originally intended. effectiveness having both nickel copper present can be rationalized nature π-activated, σ-bonded, intermediate which substitution Ni(II) for one ion classic Glaser mechanism apparently aids reductive elimination th...
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