Our recent reports of thermal fragmentation of dibenzo-7-phosphanorbornadienes to yield free singlet dialkylaminophosphinidenes has demonstrated the utility of these compounds in the synthesis of new and strained phosphorus heterocycles; however, such transformations require a large excess of reaction partner to avoid competitive oligomerization. In search of more economical routes to phosphinidene transfer from these compounds, we have pursued associative reactivity to avoid the intermediacy of free and highly reactive phosphinidenes. Dibenzo-7-phosphanorbornadiene compounds are demonstrated to be ambiphilic at the phosphorus center, allowing reaction with both electrophiles and nucleophiles to form new phosphorus-element bonds. Kinetic differences demonstrate the change in reaction mechanism from the previously reported thermal dissociative production of a free phosphinidene. A ruthenium calix[4]pyrrole system is also described that catalytically delivers <i>tert</i>-butylphosphinidene to styrene, constituting the first example of the phosphorus analog of cyclopropanation and aziridination catalysis.

Associative phosphinidene transfer from dibenzo-7-phosphanorbornadiene compounds

256th National Meeting (2018)

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