FACILE PREPARATION OF 3,7-DIAZABICYCLO [3.3.0]OCTANE AND 3,7,10-TRIHETEROCYCLIC [3.3.3]PROPELLANE RING-SYSTEMS FROM 1,5-DIAZACYCLOOCTANE 3,7-DERIVATIVES

The cyclodimerization of p-toluenesulfonamide and 3-chloro-2-(chlorome thyl)-1-propene to prepare esulfonyl)-3,7-bis(methylene)-1,5-diazacycl ooctane (1a) and its ozonation to the corresponding 3,7-dione 2a are r eported. Unusual transannular cyclizations initiated by lithium alumin um hydride treatment or bromination of 1a and oxidative coupling of th e dioxime derived from 2a are described. These reactions lead, respect ively, to the following derivatives of the little-studied 3,7-diazabic yclo[3.3.0]octane ring system: 1,5-dimethyl-3,7-diazabicyclo[3.3.0]oct ane (5), 1,5-bis(bromomethyl)-3,7-diazabicyclo[3.3.0]octane (8), and u lfonyl)-1,5-dinitro-3,7-diazabicyclo[3.3.0]octane (12). Acid-catalyzed hydration of 1a, in contrast, gives the expected 5-methyl-3,7-diazabi cyclo[3.3.1]nonan-1-ol (10). Reaction of the dibromide 8 with the nucl eophiles, sodium sulfide, sodium oxide, and sodium p-toluenesulfonamid e conveniently delivers the corresponding novel 3,7,10-triheterocyclic [3.3.3]propellanes.