Rhenium-or manganese-catalyzed transformations based on the cleavage of inactive bonds, such as carbonhydrogen and carboncarbon bonds are discussed. Such transformations are recognized as key methods to realize efficient and powerful reactions. We also reveal novel regio- and/or stereodefined cycloaddition reactions using a rhenium or manganese catalyst. Most of the catalytic activities are typical of rhenium and manganese carbonyl complexes.
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