Osmium Tetroxide-Promoted Catalytic Oxidative Cleavage of Olefins: An Organometallic Ozonolysis
Benjamin R. Travis, Radha S. Narayan and Babak Borhan*
*Department of Chemistry, Michigan State University, East Lansing, Michigan
48824, Email: babak
chemistry.msu.edu
B. R. Travis, R. S. Narayan, B. Borhan, J. Am. Chem. Soc., 2002, 124, 3824-3825.
DOI: 10.1021/ja017295g
Abstract
The OsO4-catalyzed direct oxidation of olefins via the carbon-carbon cleavage of an osmate ester by the action of oxone allows the preparation of ketones or carboxylic acids in high yields. This method should be applicable as an alternative to ozonolysis.
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proposed mechanism
Details
The document discusses a novel method for the oxidative cleavage of olefins using osmium tetroxide (OsO4) and Oxone as a co-oxidant, providing an alternative to traditional ozonolysis. This method avoids the intermediacy of 1,2-diols and addresses safety concerns associated with ozonolysis. The reaction efficiently converts various olefins into carboxylic acids or ketones with high yields. For example, cis- and trans-stilbene yield benzoic acid at 95%, while cyclohexene and cyclooctene yield adipic and suberic acids, respectively. The method also works well with substituted olefins and complex molecules, demonstrating broad applicability. The proposed mechanism involves the formation of an osmate ester, which undergoes oxidative cleavage to produce aldehydes that are further oxidized to carboxylic acids. The reaction is scalable and maintains high efficiency even with reduced amounts of OsO4. This new approach offers a mild, efficient, and safer alternative for the oxidative cleavage of olefins in organic synthesis.
Key Words
Osmium Tetroxide, Oxone, Ozonolysis, Oxidative Cleavage of Alkenes (Products: Ketones, Carboxylic Acids)
ID: J48-Y2002-1090
