title: Cyclization cascades via N-amidyl radicals toward highly functionalized heterocyclic scaffolds.
abstract: The addition of a variety of radicals to the double bond of N-(arylsulfonyl)acrylamides can trigger cyclization/aryl migration/desulfonylation cascades via amidyl radical intermediates 2. Herein, we demonstrate the synthetic utility of these intermediates in subsequent C-C and C-X bond-forming events to rapidly build up molecular complexity. First, we describe a regioselective one-pot synthesis of CF3-, SCF3-, Ph2(O)P-, and N3-containing indolo[2,1-a]isoquinolin-6(5H)-ones from N-[(2-ethynyl)arylsulfonyl]acrylamides through a multi-step radical reaction cascade. The process involves the one-pot formation of four new bonds (one C-X, two C-C, and one C-N), a formal 1,4-aryl migration, and desulfonylation of the starting material. Second, we present a one-pot synthesis of 3,3-disubstituted-2-dihydropyridinones from N-(arylsulfonyl)acrylamides and 1,3-dicarbonyl compounds. In this case, a silver-catalyzed radical cascade process involving the sequential formation of two new C-C bonds and one C-N bond, a formal 1,4-aryl migration, and desulfonylation of the starting material explains the regioselective formation of densely functionalized heterocycles in a straightforward manner. Control experiments have unraveled the key intermediates as well as the sequence of individual steps involved in these transformations.
authors.affiliation: Department of Chemistry, University of Zürich , Winterthurerstrasse 190, 8057 Zürich, Switzerland.
authors.forename: Noelia
authors.initials: N
authors.lastname: Fuentes
authors.forename: Wangqing
authors.initials: W
authors.lastname: Kong
authors.forename: Luis
authors.initials: L
authors.lastname: Fernández-Sánchez
authors.forename: Estíbaliz
authors.initials: E
authors.lastname: Merino
authors.forename: Cristina
authors.initials: C
authors.lastname: Nevado