Fragmentation of Alkoxy Radicals and Oxidative Elimination of Alicyclic Iodides

Article abstract of DOI:10.1021/jo00102a019

The azaallyl cation-mediated <4 + 3> cycloaddition with spiro<2.4>hepta-4,6-diene by the procedure of Schmid provides the tricyclic cycloadducts of general type 3.The keto bridge of the cycloadducts 17c, 21, and 22 has been cleaved by PhI(OAc)2-I2 (Suarez cleavage), which involves β-fragmentation of an alkoxy radical, to furnish iodo lactones 19, 32, and 30a,b, respectively.Subsequent oxidation of these alkyl iodides has been investigated to develop a new synthetic route for bridgehead olefins (i.e., 33) of medium-sized carbocycles.