Premium
Molybdenum Catalyzed Reactions Selectivity in Oxidations with Hydrogen Peroxide and Ammonium Molybdate
Author(s) -
Trost Barry M.,
Masuyama Yoshiro
Publication year - 1984
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.198400023
Subject(s) - chemistry , hydrogen peroxide , alcohol oxidation , aldehyde , alcohol , ketone , catalysis , selectivity , ammonium molybdate , organic chemistry , molybdate , olefin fiber , cerium , zinc
Hydrogen peroxide in conjunction with ammonium molybdate effects the epoxidation of olefins, the oxidation of secondary alcohols to ketones, and the oxidation of aldehydes to acids. By controlling pH olefin epoxidation can be suppressed in favor of alcohol oxidation. Secondary alcohols are cleanly oxidized in the presence of primary alcohols. Sterically more hindered alcohols are oxidized more rapidly than less hindered alcohols. The latter rate preference permitted selective conversion of a 17‐hydroxyl group of several steroids into a.ketone in the presence of a 3‐hydroxyl group. The chemoselective oxidation of aldehydes to carboxylic acids is another use of this inexpensive oxidation system. A rate acceleration by addition of the lanthanide salt cerium chloride is noted and attributed to enhanced rates of hydration of the aldehyde. Potential mechanisms are discussed.