76-03-9 Tandem catalysis of ring-closing metathesis/ atom transfer radical reactions with homobimetallic ruthenium-arene complexes
The tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium-indenylidene complex [(p-cymene)Ru(μ-Cl) 3 RuCl(3-phenyl-1-indenylidene)(PCy 3 )] (1) to generate active species in situ. The two catalytic processes were first carried out independently in a case study before the whole sequence was optimized and applied to the synthesis of several polyhalogenated bicyclic γ-lactams and lactones from αω-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by 1 H and 31 P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II)-Ru(III) mixed-valence compound [(p- cymene)Ru(μ-Cl) 3 RuCl 2 (PCy 3 )], which was found to be an efficient promoter for atom transfer radical reactions under t...