Iridium complex-catalyzed [2+2+2] cycloaddition of α,ω-diynes with monoynes and monoenes

被引:99
作者
Kezuka, S
Tanaka, S
Ohe, T
Nakaya, Y
Takeuchi, R
机构
[1] Aoyama Gakuin Univ, Dept Chem & Biol Sci, Sagamihara, Kanagawa 2298558, Japan
[2] Yokohama City Univ, Dept Chem, Grad Sch Integrated Sci, Kanazawa Ku, Yokohama, Kanagawa 2360027, Japan
关键词
D O I
10.1021/jo051874c
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
[Ir(cod)Cl](2)/DPPE was found to be a new catalyst for the cycloaddition of alpha,omega-diynes with monoynes to give polysubstituted benzene derivatives in high yields. Internal monoynes as well as terminal monoynes could be used. The reaction tolerates a broad range of functional groups such as alcohol, amine, alkene, ether, halogen, and nitrile. The reaction of 1,6-octadiyne derivatives with 1-alkynes gives ortho products and meta products. The regioselectivity could be controlled by the choice of ligand. The reaction with DPPE was meta selective, with meta selectivity of up to 82%. The reaction with DPPF was ortho selective, with ortho selectivity of up to 88%. We propose a mechanism to account for this regioselective cycloaddition. [Ir(cod)Cl-2]2/DPPE also catalyzed the cycloaddition of alpha-omega-diynes with 2,5-dihydrofuran to give bicyclic cyclohexadiene derivatives. The reaction with 2,3-dihydrofuran and n-butyl vinyl ether gave benzene derivatives instead of cyclohexadiene derivatives. We also propose a mechanism to account for this novel aromatization that includes cleavage of the C-O bond.
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页码:543 / 552
页数:10
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