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Shape-selective olefin epoxidation catalyzed by manganese picnic basket porphyrins

Journal Article · · Journal of the American Chemical Society; (USA)
DOI:https://doi.org/10.1021/ja00169a056· OSTI ID:6620106

The authors have previously described the synthesis and characterization of the picnic basket porphyrins, which have a rigid cavity of variable dimensions on one face of the porphyrin ring. The authors now describe conditions that result in catalytic olefin epoxidation within the cavities of a series of manganese picnic basket porphyrins. The authors have achieved substrate selectivities that reflect an interplay between the dimensions of the cavity vis-a-vis the shape of the olefin substrate. The solution to this problem involves the use of a bulky, anionic axial ligand and acetonitrile as a solvent with iodosylbenzene as the oxidant. They seem to be on the verge of predictable, shape-selective, catalytic oxygenation with a readily available, variable series of synthetic catalysts. For example, highly regioselective epoxidation of dienes should be possible.

OSTI ID:
6620106
Journal Information:
Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:13; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English

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