Catalytic Epoxidation of Alkenes by the Manganese Complex of a Reduced Porphyrinogen Macrocycle
Author(s)
Bruyneel, Frederic
Letondor, Christophe
Bastuerk, Bjorn
Gualandi, Andrea
Date issued
2012
In
Adv. Synth. Catal.
Vol
2-3
No
354
From page
428
To page
440
Subjects
Ligands Role: CAT (Catalyst use) USES (Uses) (effect of added ligands on epoxidn. yield prepn. and structure of manganese complexes of a reduced porphyrinogen macrocycle and catalytic activity for the epoxidn. of alkenes) Crystal structure Molecular structure (of manganese complexes of a reduced porphyrinogen macrocycle) Epoxidation Epoxidation catalysts (prepn. and structure of manganese complexes of a reduced porphyrinogen macrocycle and catalytic activity for the epoxidn. of alkenes) Alkenes Role: RCT (Reactant) RACT (Reactant or reagent) (prepn. and structure of manganese complexes of a reduced porphyrinogen macrocycle and catalytic activity for the epoxidn. of alkenes) Epoxides Role: SPN (Synthetic preparation) PREP (Preparation) (prepn. and structure of manganese complexes of a reduced porphyrinogen macrocycle and catalytic activity for the epoxidn. of alkenes) Diastereoselective synthesis (stereoselective epoxidn. of cis-stilbene and a cholestane deriv. prepn. and structure of manganese complexes of a reduced porphyrinogen macrocycle and catalytic activity for the epoxidn. of alkenes) manganese reduced porphyrinogen macrocycle complex prepn crystal mol structure alkene epoxidn manganese porphyrinogen complex catalyst apical ligand screen epoxide prepn stilbene acetoxycholestane stereoselective epoxidn
Abstract
The present paper details the first application of a fully reduced meso-octamethylporphyrinogen macrocycle as an effective ligand for simple operative manganese-catalyzed alkene epoxidn. The efficiency of the novel catalyst was detd. in the presence of various oxidants, apical ligands and acidic/basic additives. Higher reactivity was found in favor of electron-rich alkenes, whereas an electron-deficient conjugated alkene appeared to be a poor substrate in the screening. Sulfur additives were active as apical ligands, whereas nitrogen-contg. additives influenced the reactivity only moderately. Cis-Stilbene and 3?-acetoxy-5-cholestene were epoxidized in a stereoselective manner. The x-ray structures of the new manganese complexes were detd. and showed a rigid planar coordination geometry of the satd. macrocyclic ligand to the metal center. [on SciFinder(R)]
Publication type
journal article