Reactions of transition metal carbonyl anions with 2-(1-bromoalkylidene)thiazolidin-4-ones: halogenophilic attack or deprotonation

Bromophilic attack by the transition metal carbonyl anion, [Re(CO)5]Na (pKa = 21.1), on 2-(1-bromoalkylidene)thiazolidin-4-ones is significantly faster than abstraction of an acidic lactam hydrogen (pKa ∼17-18), when the generated carbanion is stabilized by an α-CN or α-PhCO group. The bromophilic reaction of 2-(1-bromoalkylidene)thiazolidin-4-one, having an α-CN electron-withdrawing group, resulted in formation of a new metallacyclic anionic complex. With less reactive vinyl bromides, containing an α-CONHPh or α-CO2Et group, only deprotonation is observed. The role of the metal carbonyl anion is highlighted by a comparison with the 9-methylfluorenide carbanion (pKa of 9-methylfluorene is 22.3), which reacts exclusively via a deprotonation pathway.

Graphical abstractBromophilic attack by the metal carbonyl anion, [Re(CO)5]− Na+; pKa of [Re(CO)5]H = 21.1, on 2-(1-bromoalkylide-ne)thiazolidin-4-ones (Z = CN and COPh) is significantly faster than abstraction of an acidic lactam hydrogen (pKa ∼17-18).Download full-size image