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Applications of 5-Endo-trigonal Cyclization:  Construction of Compounds Relevant to the Synthesis of Prostaglandins and Methyl epi-Jasmonate

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journal contribution
posted on 26.03.1999 by Mousumi Sannigrahi, Darrin L. Mayhew, Derrick L. J. Clive
Silane 15, easily constructed by simple methods, undergoes a cascade of radical reactions when treated with a stannane to afford the bicyclic 1,2-oxasiloles 16, with the major isomer having the ester group anti to the O−Si unit. This isomer was elaborated via 19 into 6, a deoxy derivative of the Corey lactone. In a related sequence, ketone 24 was converted into silane 35; this, too, underwent the radical cascade to afford the highly substituted 1,2-oxasiloles 36. Again the major isomer had the ester and O−Si units in an anti relationship. Elaboration of 36 (major isomer) gave the Corey lactone derivative 7. A key intermediate (32) in this second sequence was also prepared in optically pure form by starting with 2-deoxy-d-ribose. Compound 19 was converted into 8, a sequence that constitutes a formal synthesis of methyl (±)-epi-jasmonate. Two examples were found of selective silylation of a propargylic secondary hydroxyl in the presence of an ordinary secondary hydroxyl.