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Selectivity Manipulation of Bicyclization Reactions of 1,5-Bis(1,2-allenylketone)s: Pd versus Rh and Electronic Effect

Authors

  • Dr. Youqian Deng,

    1. Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang (P. R. China), Fax: (+86) 21-64167510
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  • Prof. Dr. Chunling Fu,

    1. Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang (P. R. China), Fax: (+86) 21-64167510
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  • Prof. Dr. Shengming Ma

    Corresponding author
    1. Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang (P. R. China), Fax: (+86) 21-64167510
    • Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang (P. R. China), Fax: (+86) 21-64167510
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Abstract

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Select Rh! The rhodium(I)-catalyzed double cyclization of 1,5-bis(1,2-allenylketone)s gives TNF-α inhibitor (A)-type skeletons at room temperature in acetone or 1,2-dichloroethane (DCE, see scheme; Ts=Tosyl). Compared with [PdCl2(MeCN)2], [RhCl(CO)2]2 shows excellent selectivity towards the nonaromatic C[DOUBLE BOND]C bond. The selectivity of unsymmetrical substrates can be controlled by the electronic effect.

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