7- and 8-membered ring sugars and related systems : 7-Membered rings from diolefins derived from dioxepans via double michael condensations

The possibilities of cyclisation to 7-membered ring sugars containing nitro- and cyano-functions via double Michael condensations of diolefins derived from sugar dioxepans was investigated. With nitromethane cyclised products were obtained while with the larger ethyl cyanoacetate and malononitrile only one double bond was attacked without cyclisation. Treatment of the diolefins with excess ammonia resulted in cyclisation to novel heterocyclic systems containing oxygen and nitrogen often of known stereochemistry; with butylamine no cyclisation occurred. Treatment with hydrogen sulphide also resulted in cyclisation to novel heterocyclic systems containing sulphur and oxygen often of known stereochemistry. In these systems cyclisation only occurs with the smaller reagents.