Chemistry of Monoorganopalladium Complexes Relevant to Catalysis

Akio Yamamoto; Yoshihito Kayaki; Kazuhiro Nagayama; Isao Shimizu

doi:10.1055/s-2000-6645

Synlett 2000; 2000(7): 0925-0937
DOI: 10.1055/s-2000-6645

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Chemistry of Monoorganopalladium Complexes Relevant to Catalysis

Akio Yamamoto^* , Yoshihito Kayaki, Kazuhiro Nagayama, Isao Shimizu

^*Department of Applied Chemistry, Graduate School of Science and Engineering, and Advanced Research Institute for Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo, 169-8555 (Japan); Fax (81)-3-32 04-62 74; E-mail: akioyama@mn.waseda.ac.jp

Abstract

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Neutral and cationic organopalladium complexes have been prepared as models for active intermediates involved in palladium-catalyzed reactions. Comparison of the reactivities of the neutral and cationic complexes revealed the much higher reactivities of the latter toward β-elimination and olefin or CO insertion. Generation of the solvent-coordinated hemilabile site on the cationic organopalladium complexes was indicated as a dominant factor in enhancing the reactivities. Utilizing the reactivity of an acylpalladium complex toward hydrogen, a novel, selective, and environmentally benign hydrogenation process catalyzed by palladium complexes to give various aldehydes has been developed.

organopalladium complex - β-elimination - insertion - silver salts - hydrogenation of carboxylic acids

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