Abstract: | The substitution pattern of the 2‐phosphabicyclo2.2.2]octene framework and the skeleton itself were varied to obtain new cycloadducts usable in phosphorylations and to study their ability to undergo fragmentation. Thus, an N‐methyl and several P‐trialkylphenyl derivatives ( 7 and 9 , respectively) were synthesized, together with two diaza species ( 8 ) whose stereostructure was evaluated by single crystal X‐ray analysis. Mechanistic studies on the UV light‐mediated photolysis of the P‐aryl phosphabicyclooctenes ( 9 ) in the presence of methanol supports the suggestion of a novel addition–elimination reaction path. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:626–632, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10052 |