title: Expeditious diastereoselective synthesis of elaborated ketones via remote Csp3-H functionalization.
abstract: The quest for selective C-H functionalization reactions, able to provide new strategic opportunities for the rapid assembly of molecular complexity, represents a major focus of the chemical community. Examples of non-directed, remote Csp3-H activation to forge complex carbon frameworks remain scarce due to the kinetic stability and thus intrinsic challenge associated to the chemo-, regio- and stereoselective functionalization of aliphatic C-H bonds. Here we describe a radical-mediated, directing-group-free regioselective 1,5-hydrogen transfer of unactivated Csp3-H bonds followed by a second Csp2-H functionalization to produce, with exquisite stereoselectivity, a variety of elaborated fused ketones. This study demonstrates that aliphatic acids can be strategically harnessed as 1,2-diradical synthons and that secondary aliphatic C-H bonds can be engaged in stereoselective C-C bond-forming reactions, highlighting the potential of this protocol for target-oriented natural product and pharmaceutical synthesis.
authors.affiliation: Department of Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland.
authors.forename: Wei
authors.initials: W
authors.lastname: Shu
authors.affiliation: Department of Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland.
authors.forename: Adriana
authors.initials: A
authors.lastname: Lorente
authors.affiliation: Departamento de Química Orgánica I, Universidad del Pais Vasco, Apdo 1072, CP-20080 Donostia-San Sebastián, Spain.
authors.forename: Enrique
authors.initials: E
authors.lastname: Gómez-Bengoa
authors.affiliation: Department of Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland.
authors.forename: Cristina
authors.initials: C
authors.lastname: Nevado