The Advantages of Cyclic Over Acyclic Carbenes To Access Isolable Capto-Dative C-Centered Radicals.

A cyclic and an acyclic di(amino)carbene as well as a cyclic and an acyclic (alkyl)(amino)carbene cleanly react with benzoyl chloride to give the corresponding adducts 1+cyc , 1+acy , 2+cyc , and 2+acy , respectively. The reduction of 1+cyc and 2+cyc derived from cyclic carbenes affords the corresponding radicals 1cyc and 2cyc that are stable at room temperature. In contrast, radicals 1acy and 2acy , derived from acyclic carbenes, cannot be isolated. It is shown that 1acy is as thermodynamically stabilized as its cyclic counterpart 1cyc , but its instability is the result of β-hydrogens of the nitrogen substituent, along with the enhanced flexibility around C-N bonds, which allow for a H. -migration-elimination process. Radical 2acy is thermodynamically unstable, and undergoes disproportionation into the corresponding iminium 2+acy and enolate 2-acy . This is due to the excessive steric hindrance, which prevents electron-delocalization on the NCCO fragment, and thus, the capto-dative stabilization. This work suggests general guidelines for the design of highly persistent (amino)(carboxy)radicals, especially by emphasizing the key advantage of cyclic patterns.