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Control of Epoxidation Enantioselectivity by Axial Ligation in Manganese Chiroporphyrins with Diastereotopic Faces
Author(s) -
Liu ShuQing,
Pécaut Jacques,
Marchon JeanClaude
Publication year - 2002
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 - 10.1002/1099-0682(200207)2002:7<1823::aid-ejic1823>3.0.co;2-d
Subject(s) - chemistry , manganese , catalysis , ligand (biochemistry) , dichloromethane , pyridine , medicinal chemistry , block (permutation group theory) , stereochemistry , organic chemistry , receptor , geometry , biochemistry , mathematics , solvent
A manganese(III) chiroporphyrin with alternate pentafluorophenyl and chiral cyclopropyl meso‐substituents in the αFαF conformation has been shown by X‐ray crystallography to have its chloro axial ligand predominantly on the non‐chiral β face. Epoxidation of 1,2‐dihydronaphthalene by iodosylbenzene induced by the neat catalyst in dichloromethane solution shows a twofold increase in enantioselectivity relative to the same reaction in the presence of pyridine. These observations suggest that the location of the chloro ligand on the β face can block that face from participating in catalytic epoxidation, and direct the reaction to take place on the chiral α face. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)