Unimolecular Fragment Coupling: A New Bond-Forming Methodology via the Deletion of Atom(s).

Unimolecular fragment coupling (UFC) is defined as a reaction format, wherein atom(s) located in the middle of a molecule are extruded, and the remaining fragments are coupled. UFC is a potentially powerful strategy that is an alternative to transition-metal-catalyzed cross-coupling because the target chemical bond is formed in an intramolecular fashion, which is inherently beneficial for chemoselectivity and stereoselectivity issues. In this Perspective, we will present an overview of the recent advances in UFC reactions, which encompass those proceeding through the elimination of CO 2 , CO, SO 2 , isocyanates, N 2 , or single atoms primarily via transition metal catalysis.