Patai S., Rappoport Z. 1997 The chemistry of functional groups. The chemistry of dienes and polyenes. V. 1 / 0619 652

Reactions involving ceric ammonium nitrate (CAN) as oxidant give nitrates instead of acetates or methyl ethers as final trapping products8,55,56. Oxidation of the adduct allyl radicals 48 (Scheme 4) appears in this case to follow a ligand transfer mechanism rather than a stepwise electron transfer/nucleophilic addition sequence. The oxidation of ethyl acetoacetate in the presence of butadiene, for example, leads to adduct radical 74, which is trapped by CAN to form the two possible products 75 and 76 in high yield but low selectivity (equation 31). A similar sequence has been used starting from silyloxycyclopropanes, which yield ˇ-carbonylalkyl radicals after CAN oxidation. Addition to butadiene and trapping with CAN again forms a mixture of nitrates, which have in this case been used as substrates for the palladium(II) catalyzed coupling with carbonand nitrogen-centered nucleophiles56.

For completeness, it must also be noted that the oxidation of enolizable compounds and intermediate allyl radicals can be achieved electrochemically54b. The resulting product mixtures, however, proved much more complex as compared to oxidation by transition metal salts.

VII. ACKNOWLEDGEMENT

Generous support by the Fonds der Chemischen Industrie is gratefully acknowledged.

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