ChemInform Abstract: Ruthenium-Catalyzed Carbonylative Cycloaddition Reactions Involving Carbonyl and Imino Groups as Assembling Units

This paper describes carbonylative cycloaddition reactions catalyzed by Ru3(CO)12. Ru3(CO)12 was found to catalyze an intramolecular Pauson–Khand-type reaction. Carbonylative cycloaddition reactions involving a carbonyl group in aldehydes, ketones, and esters as a two-atom assembling unit were also achieved in the presence of Ru3(CO)12 as the catalyst. The reaction of 5-hexyn-1-al and 6-heptyn-1-al derivatives with CO in the presence of Ru3(CO)12 resulted in cyclocarbonylation from which bicyclic α, β-unsaturated lactones were obtained. Intermolecular [2 + 2 + 1] carbonylative cycloaddition of alkenes, ketones, and CO was also catalyzed by Ru3(CO)12 as the catalyst to give saturated γ-lactone derivatives. Simple ketones were not applicable, but ketones having a CO or CN group at the α-position served as a good substrate. These reactions could be extended to carbonylative cycloaddition of the corresponding imines leading to γ-butyrolactam derivatives. The [4 + 1] carbonylative addition of α,β-unsaturated imines leading to unsaturated γ-lactams was achieved with Ru3(CO)12. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 201–212; 2008: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20149