Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium-arene complexes

被引:22
作者
Borguet, Yannick [1 ]
Sauvage, Xavier [1 ]
Zaragoza, Guillermo [2 ]
Demonceau, Albert [1 ]
Delaude, Lionel [1 ]
机构
[1] Univ Liege, Macromol Chem & Organ Catalysis Lab, Inst Chim B6A, B-4000 Liege, Belgium
[2] Univ Santiago de Compostela, Unidade Raios X, Santiago De Compostela 15782, Spain
来源
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY | 2010年 / 6卷
关键词
Grubbs catalyst; indenylidene ligands; Kharasch reaction; microwave heating; olefin metathesis; MECHANISTICALLY DISTINCT REACTIONS; INDENYLIDENE COMPLEXES; ONE-POT; OLEFIN ISOMERIZATION; OPENING-METATHESIS; CARBENE COMPLEXES; KHARASCH REACTION; CHEMISTRY; SEQUENCE; LACTAMS;
D O I
10.3762/bjoc.6.133
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
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.
引用
收藏
页码:1167 / 1173
页数:7
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