Olefin Epoxidation by an Intermediate Formed in the Metal Ion Catalyzed Oxygenation of Azibenzil

Journal of the American Chemical Society

Volumn 102, Issue 6, 1980, Pages 2129-2131

  Ryang, Hong Son ^a   Foote, Christopher S ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0345695773     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00526a081     Document Type: Letter

References (42)

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20. Pd(ll) compounds [Pd(OAc2, PdCI2, (PhCN)2PdCI2] were found to be the most effective catalysts for the reaction. Other catalysts [CuO, Cu2CI2, Cu(OAc)2, Cu(acac)2, and Ni(acac)2] need longer times and higher temperatures to accomplish the reaction, and yields were lower than those shown in Table I. It was also found that other diazo compounds such as diphenyldiazomethane and diazoacetophenone give olefin epoxidation, with some of the catalysts, but in lower yield than 1. Details will be reported elsewhere.
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34. It has been shown that (PhCN)2PdCI2 reacts with diazoacetophenone to give an oxo-7r-allyl-palladium complex; see N. Yoshimura, S.-l. Murhashi, and I. Moritani, J. Organomet. Chem., 52, C58 (1973). In our hands, complex 5 is air stable at room temperature, but thermal decomposition in the presence of 02 occurs to give benzil and benzonitrile. The IR spectrum showed a strong peak at 320 cm-1 owing to the Pd-CI bond and had no characteristic band due to the carbonyl group. The results suggest that 5 is probably the oxo-7r-allyl complex as shown below.
35. The reaction was checked by GC and LC at ’30, ’10, 0, 10, and 20 °C after removal of 02 by flushing with N2. Below 10°, no epoxidation was observed.
36. An alternative path in which N2 evolution and 02 attack occur simultaneously in intermediate 7 might be considered. However, 6 is a preferable formulation because the formation of benzophenone as an oxidation product would require the formation of a free ketocarbene which could be formed by a nucleophilic attack of acetonitrile on 6, but not on 7. This formulation is consistent with the effects of base on the reaction of Cu-(acac)2 with diazoacetophenone22 and the instability of carbene complexes to nucleophiles.23
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