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C−C Coupling Reactions of (Sulfene)ruthenium Complexes with Enolates
Author(s) -
Schenk Wolfdieter A.,
Bezler Jürgen
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199805)1998:5<605::aid-ejic605>3.0.co;2-h
Subject(s) - chemistry , ruthenium , carbene , acetonitrile , medicinal chemistry , ligand (biochemistry) , alkylation , diazomethane , sulfur , stereochemistry , catalysis , organic chemistry , biochemistry , receptor
Abstract Sulfene complexes [CpRu(PR′ 3 ) 2 (RHC=SO 2 )]PF 6 ( 2a − d ) are obtained from the corresponding sulfur dioxide complexes 1a − c and diazomethane or ‐ethane. Reaction of [CpRu(dppm)(SO 2 )]Cl ( 1d ) and phenyldiazomethane gives the chlorobenzylsulfinato complex [CpRu(dppm)(SO 2 CHPhCl)] ( 3 ). Alternatively, 2a may be synthesized by sulfur dioxide addition to the carbene complex [CpRu(dppm)(CH 2 )]PF 6 ( 5 ) which, in turn, is obtained from the corresponding methyl complex [CpRu(dppm)(CH 3 )] and [Ph 3 C]PF 6 . Treatment of 2a − d or 3 with the enolates of cyclic 2‐methyl‐1,3‐diketones, methyl malonates, open‐chain cyano or β‐oxo esters, and cyclic β‐oxo esters gives the C−C coupling products 6a , b , 7a−e , 8a−c , 9a − c in high yields and, in one case, with high diastereoselectivity as well. The functionalized sulfinate ligands thus formed may be alkylated and subsequently removed from the metal center by ligand substitution with acetonitrile. After MeCN/SO 2 exchange, the ruthenium complex can be recycled.