Synthesis of 3,3-Spirocyclic 2-Phosphonoindolines via a Dearomative Addition of Phosphonyl Radicals to Indoles.

The diastereoselective synthesis of α-amino phosphonate derivatives embedded in spirocyclic indolines is reported. The present method proceeds via the dearomative addition of phosphonyl radicals at the C2-position of the indole nucleus in oxidative conditions followed by the intramolecular trapping of the resulting carbocation before rearomatization. trans-3,3-Spirocyclic 2-phosphonoindolines were thus obtained.

Radical-Mediated Dearomatization of Indoles with Sulfinate Reagents for the Synthesis of Fluorinated Spirocyclic Indolines.

The dearomative introduction of trifluoromethyl and 1,1-difluoroethyl radicals, generated from their corresponding sulfinate salts, into the C2 position of indole derivatives allows the diastereoselective synthesis of three-dimensional 3,3-spirocyclic indolines over C-H functionalized indoles.