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Allylic CH Oxidation versus Epoxidation of 2‐Cyclohexenols, Catalyzed by Chromium‐ and Manganese‐Substituted Polyoxometalates and Salen Complexes
Author(s) -
Adam Waldemar,
Herold Marike,
Hill Craig L.,
SahaMöller Chantu R.
Publication year - 2002
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200203)2002:5<941::aid-ejoc941>3.0.co;2-a
Subject(s) - chemistry , manganese , allylic rearrangement , catalysis , chemoselectivity , diastereomer , chromium , medicinal chemistry , cinnamyl alcohol , metal salen complexes , polyoxometalate , polymer chemistry , stereochemistry , organic chemistry , selectivity
2‐Cyclohexenol ( 1 ) is oxidized chemoselectively to 2‐cyclohexenone ( 2a ) by the α‐Keggin chromium‐substituted polyoxometalate (POM) Ia as the catalyst and iodosobenzene as the oxygen source. For the chromium(salen) catalyst IIa the same chemoselectivity in favor of allylic CH oxidation is observed. The manganese‐substituted POM Ib and the manganese(salen) complex IIb , however, afford appreciable amounts of the epoxy alcohol 2b . For the stereolabeled 5‐ tert ‐butyl‐2‐cyclohexenols 5 , the diastereoselectivity of the epoxidation was appreciable ( syn:anti 82:18) in the case of the manganese(salen) complex IIb with the cis isomer, while the manganese‐substituted POM Ib exhibited no syn versus anti π‐facial differentiation for the cis or trans diastereomer of the cyclohexenol 5 . The observed syn hydroxy directivity for the manganese(salen) complex IIb is rationalized in terms of optimal hydrogen bonding between the Mn V oxo complex IIb and the trans diastereomer of the allylic alcohol substrate 5 . (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)