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Oxidation of Glycals with Hydrogen Peroxide
Author(s) -
Mostowicz Danuta,
Jurczak Margarita,
Hamann HansJurgen,
Höft Eugen,
Chmielewski Marek
Publication year - 1998
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/(sici)1099-0690(199811)1998:11<2617::aid-ejoc2617>3.0.co;2-0
Subject(s) - chemistry , hydrogen peroxide , glucal , allylic rearrangement , anomer , enantioselective synthesis , yield (engineering) , organic chemistry , medicinal chemistry , catalysis , materials science , metallurgy
Abstract Tri‐ O ‐acetyl‐D‐glucal ( 8 ) treated with a mixture of hydrogen peroxide–molybdenum trioxide undergoes a Ferrier rearrangement to form 2,3‐unsaturated anomeric hydroperoxides 14 and 15 . Tri‐ O ‐acetyl‐D‐galactal ( 10 ) and tri‐ O ‐benzyl‐D‐glucal ( 9 ), under the same conditions, afford the hydroperoxides in a low yield, whereas tri‐ O ‐benzyl‐D‐galactal ( 11 ) does not produce any unsaturated hydroperoxide. 2,3‐Unsaturated anomeric hydroperoxides of α‐ and β‐D‐ erythro ‐ and α‐D‐ threo ‐ 19 , ‐20 , and ‐ 24 , respectively, were used for the enantioselective epoxidation of prochiral allylic alcohols 25‐27 and oxidation of sulfides 28 and 29 to give stereoselectivities of up to 50% enantiomeric excess.