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Asymmetric oxidation of sulfides catalyzed by chiral (salen)Mn(III) complexes with a pyrrolidine backbone
Author(s) -
Gao Aiping,
Wang Mei,
Shi Jicheng,
Wang Dongping,
Tian Wei,
Sun Licheng
Publication year - 2006
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.1121
Subject(s) - chemistry , pyrrolidine , thioanisole , steric effects , catalysis , medicinal chemistry , substituent , sulfide , selectivity , enantioselective synthesis , metal salen complexes , trimethylamine , aryl , organic chemistry , alkyl
Abstract Catalytic properties of a series of chiral (pyrrolidine salen)Mn(III) complexes for asymmetric oxidation of aryl methyl sulfides were evaluated. Moderate activity, good chemical selectivity and low enantioselectivity were attained with iodosylbenzene as a terminal oxidant. Enantioselectivity of sulfide oxidation was affected slightly by polar solvent and the sulfoxidation carried out in THF for thioanisole and in CH 3 CO 2 Et for electron‐deficient sulfides gave better enatioselctivities. The addition of the donor ligand PPNO (4‐phenylpyridine N ‐oxide) or MNO (trimethylamine N ‐oxide) only has a minor positive effect on the enantioselectivity. Also explored was the steric effect of the N aza ‐substituent in the backbone of (pyrrolidine salen)Mn(III) complexes on the enantioselectivity of sulfide oxidation. The sulfides' access pathway is discussed based on the catalytic results. Copyright © 2006 John Wiley & Sons, Ltd.