The Diene Effect: The Design, Development, and Mechanistic Investigation of Metal‐Catalyzed Diene‐yne, Diene‐ene, and Diene‐allene [2+2+1] Cycloaddition Reactions

Department of Chemistry, Stanford University, Stanford, CA 94305, USA, Fax: +1-650-725-0259
European Journal of Organic Chemistry (Impact Factor: 3.07). 01/2010; 2010(1):19 - 32. DOI: 10.1002/ejoc.200900929


Metal-catalyzed diene-yne, diene-ene, and diene-allene [2+2+1] cycloaddition reactions provide new methods for the facile construction of highly functionalized five-membered rings. These reactions can be conducted with a variety of substrate substitution patterns and functional groups and often in the absence of solvent. The special reactivity of dienes, a key to enabling or enhancing the effectiveness of the [2+2+1] and other reactions, is significantly different from that of alkynes, alkenes, or allenes. For example, the [2+2+1] reaction of a diene-yne is accelerated compared to that of the corresponding ene-yne. An even more dramatic "diene effect" is found with diene-enes and diene-allenes. While bis-enes and ene-allenes are not reported to yield [2+2+1] cycloadducts, the related diene-enes and diene-allenes undergo efficient [2+2+1] cycloadditions, providing new routes to cyclopentanones and alkylidenecyclopentanones. Mechanistic studies suggest that the unique reactivity observed with dienes arises from their participation in the putative rate-determining reductive elimination step by providing an additional energy-lowering coordination site for the transition metal catalyst.

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Available from: Mitchell P Croatt
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