Palladium-catalyzed oxygenation of unactivated sp3 C-H bonds

Journal of the American Chemical Society

Volumn 126, Issue 31, 2004, Pages 9542-9543

  Desai, Lopa V ^a   Hull, Kami L ^a   Sanford, Melanie S ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

METHANE; PALLADIUM; TRANSITION ELEMENT;

ARTICLE; CATALYSIS; CHEMICAL BOND; CHEMICAL STRUCTURE; OXIDATION; OXYGENATION; STOICHIOMETRY; SYNTHESIS;

EID: 3543057683     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja046831c     Document Type: Article

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24. 3 C-H acetoxylation (see Supporting Information, Table S1).
25. Notably, the analogous OH oxime underwent oxidative cleavage to the ketone under the reaction conditions, and the ketone showed no reactivity towards Pd(II)-catalyzed acetoxylation.
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29. Stereochemistry was assigned by standard analysis of the coupling constants of the hydrogen α to the acetate (see Supporting Information).
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31. The observed stereochemistry is consistent with either (i) initial C-H activation at the axial position followed by reductive elimination with inversion of configuration or (ii) equatorial C-H activation followed by reductive elimination with retention. Experiments aimed at distinguishing these mechanistic possibilities are currently underway.