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Catalytic Epoxidation of Alkenes by the Manganese Complex of a Reduced Porphyrinogen Macrocycle
Author(s) -
Bruyneel Frederic,
Letondor Christophe,
Bastürk Bjorn,
Gualandi Andrea,
Pordea Anca,
StoeckliEvans Helen,
Neier Reinhard
Publication year - 2012
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201100433
Subject(s) - chemistry , alkene , reactivity (psychology) , manganese , ligand (biochemistry) , catalysis , stereoselectivity , polymer chemistry , metal , substrate (aquarium) , sulfur , medicinal chemistry , stereochemistry , photochemistry , organic chemistry , medicine , biochemistry , oceanography , alternative medicine , receptor , pathology , geology
The present paper details the first application of a fully reduced meso ‐octamethylporphyrinogen macrocycle as an effective ligand for simple operative manganese‐catalyzed alkene epoxidation. The efficiency of the novel catalyst was determined in the presence of various oxidants, apical ligands and acidic/basic additives. Higher reactivity was found in favour of electron‐rich alkenes, whereas an electron‐deficient conjugated alkene appeared as a poor substrate in the screening. Sulfur additives were active as apical ligands, whereas nitrogen‐containing additives influenced the reactivity only moderately. cis ‐Stilbene and 3β‐acetoxy‐5‐cholestene were epoxidized in a stereoselective manner. The X‐ray structures of the new manganese complexes were determined and showed a rigid planar coordination geometry of the saturated macrocyclic ligand to the metal centre.