[en] The tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium-indenylidene complex [(p-cymene)Ru(mu-Cl)(3)RuCl(3-phenyl-1-indenylidene)(PCy3)] (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 gamma-lactams and lactones from alpha,omega-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by H-1 and P-31 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(mu-Cl)(3)RuCl2(PCy3)], which was found to be an efficient promoter for atom transfer radical reactions under the adopted experimental conditions.
Disciplines :
Chemistry
Author, co-author :
Borguet, Yannick ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique
Sauvage, Xavier ; Université de Liège - ULiège > Centre de recherches du cyclotron
Zaragoza, Guillermo
Demonceau, Albert ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique
Delaude, Lionel ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie macromoléculaire et catalyse organique
Language :
English
Title :
Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium-arene complexes
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