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Chemistry. 2001 Apr 17;7(8):1589-95. doi: 10.1002/1521-3765(20010417)7:8<1589::aid-chem15890>3.0.co;2-1.

Advances in the Pauson-Khand reaction: development of reactive cobalt complexes.

Chemistry (Weinheim an der Bergstrasse, Germany)

T Sugihara, M Yamaguchi, M Nishizawa

Affiliations

  1. Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Japan. [email protected]

PMID: 11349898 DOI: 10.1002/1521-3765(20010417)7:8<1589::aid-chem15890>3.0.co;2-1

Abstract

Three conceptually new methods employing reactive cobalt carbonyl complexes have been developed for the Pauson-Khand reaction. The first method involves activation of alkyne-dicobalt hexacarbonyls with "hard" Lewis bases. Primary amines dramatically promote the stoichiometric Pauson-Khand reaction. The active cobalt complexes produced in the system exhibit high reducing ability. The second method involves activation of dicobalt octacarbonyl with less electron-donating "hard" Lewis bases such as 1,2-dimethoxyethane and water. These Lewis bases were successfully utilized as a promoter for the catalytic Pauson-Khand reaction. The third method employs methylidynetricobalt nonacarbonyl cluster, which exhibits high reactivity in the catalytic Pauson-Khand reaction in the absence of activator. This may be due to facile coordination of the substrate to the metal center through dissociative and associative mechanisms and/or cleavage of one of the cobalt-cobalt bonds.

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