O-Acylated 2,2,6,6-tetramethylpiperidine-N-oxyls (abbr. O-AcylTEMPOs) are
easily available and stable carboxylic derivatives, but their utility in organic synthesis is
unexplored in contrast to analogues, such as the N-methoxy-N-methylamides, known as
Weinreb amides. Especially, the O–N unit of the O-acylTEMPOs dictates a fairly electronwithdrawing
character for the carbonyl function. This enhances the reactivity and stability
of the resulting enolate ions. Accordingly, O-acylTEMPOs allow various transformations
and this review encompasses seven topics: (1) Reactivity of O-acylTEMPOs towards nucleophiles
and chemoselective transformations, (2) Reactivity of anionic species derived
from O-acylTEMPOs, (3) E-Selective Knoevenagel condensation of acetoacetylTEMPOs
and synthesis of furans, (4) Electrocyclization of 2,4-dienones derived from acetoacetic
derivatives and 2-substituted enals, (5) Diastereoselective addition of amide anion to O-(2-alkenoyl)TEMPOs
and β-amino acid synthesis, (6) Thermolysis of O-acylTEMPOs, and (7) Applications for Umpolung reactions
using O-benzoylTEMPOs, useful for the electrophilic amination of alkenes and alkynes.
Copper‐Catalyzed Enantio‐ and Diastereoselective Addition of Silicon Nucleophiles to 3,3‐Disubstituted Cyclopropenes
