摘要：

Novel catalytic reactions via ruthena- or rhodacyclic intermediates have been developed by our research group. We initiated our study from (1) ruthenium-catalyzed [2+2] cycloaddition of alkynes with alkenes, followed by developing (2) intramolecular Pauson-Khand-type reaction of 1,6-enynes, (3) hydroquinone synthesis, (4) cyclocotrimerization reactions, and (5) codimerization of styrenes with ethylene. Another approach to construct novel functional monomers, such as cyclopentenones, pyranopyrandiones, and substituted phenols, involves cleavage of carbon-carbon bonds in cyclobutenediones, cyclopropenones, and cyclobutenones. All reactions may proceed with high atom-efficiency via ruthena- or rhodacyclic intermediates, represented by ruthenacyclopentene, (maleoyl)ruthenium, and rhodacyclopentenone intermediates. In addition, rhodium-catalyzed [2+2+2] cocyclization of alkynes with isocyanates as well as novel ruthenium-catalyzed [2+2+1] cocyclization of alkynes, isocyanates, and carbon monoxide have been disclosed.1 Introduction2 Ruthenium-Catalyzed Cycloaddition of Alkynes with Alkenes2.1 [2+2] Cycloaddition of Alkynes with 2-Norbornenes 2.2 Intramolecular Pauson-Khand-Type Reaction of Enynes with Carbon Monoxide 2.3 Cross-Carbonylation of Alkynes with 2-Norbornenes or Electron-Deficient Alkenes to Hydroquinones2.4 Synthesis of Benzenepolycarboxylates by Cross-Benzannulation of Acetylenedicarboxylates with Allylic Compounds2.5 [2+2+2] Cocyclization of Three Different Alkynes2.6 Regio- and Stereoselective Dimerization of Styrenes and Linear Codimerization of Styrenes with Ethylene3 Ruthenium- and Rhodium-Catalyzed Cleavage of C-C Bonds Leading to Reconstructive Synthesis of Novel Functional Monomers 3.1 Ru-Catalyzed Selective Monodecarbonylative Coupling of Cyclobutenediones with Alkenes to Cyclopentenones 3.2 Ru-Catalyzed Carbonylative Dimerization of Cyclopropenones and Cross-Carbonylation of Cyclopropenones with Alkynes to Pyranopyrandiones 3.3 Ru- and Rh-Catalyzed Ring-Opening Reactions of Cyclobutenones 3.4 Rh-Catalyzed Direct Synthesis of Substituted Phenols from Cyclobutenones and Electron-Deficient Alkenes 4 Ruthenium- and Rhodium-Catalyzed Cocyclization of Alkynes and Isocyanates4.1 Rh-Catalyzed Cyclocotrimerization of Alkynes and Isocyanates to 2-Pyridones or Pyrimidine-2,4-diones4.2 Ru-Catalyzed [2+2+1] Cocyclization of Alkynes, Isocyanates, and Carbon Monoxide 5 Summary

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