Dual Co/Photoredox‐Catalyzed Regio‐ and Stereoselective Synthesis of Highly Functional 1,3‐Dienes
Abstract
Abstract A dual Co/photoredox catalytic coupling of 1,3‐enynes and α,ß‐unsaturated aliphatic aldehydes and ketones has been developed that creates access to highly functional 1,3‐diene synthons through a regio‐ and stereoselective carbon‐carbon coupling process. The scope of the process features diverse functionalized scaffolds with a high degree of molecular complexity. The synthetic utility of these 1,3‐dienes is demonstrated including a telescoped, one‐pot approach using an alkynyl cyclic carbonate as a 1,3‐enyne surrogate offering direct access to the 1,3‐diene product. Mechanistic analysis involving control reactions, deuterium labeling studies and DFT calculations are in line with the in situ formation of a Co─H species and an outer‐sphere coupling pathway in which a regio‐ and stereoselective coupling occurs between a dienyl radical and carbonyl species.
Article Details
Authors (9)
Balázs L. Tóth
Institute of Chemical Research of Catalonia (ICIQ) Barcelona Institute of Science and Technology (BIST) Av. Països Catalans 16 Tarragona 43007 Spain
Alejandro Delgado
Institute of Chemical Research of Catalonia (ICIQ) Barcelona Institute of Science and Technology (BIST) Av. Països Catalans 16 Tarragona 43007 Spain
Debasish Ghorai
Institute of Chemical Research of Catalonia (ICIQ) Barcelona Institute of Science and Technology (BIST) Av. Països Catalans 16 Tarragona 43007 Spain
Diego Meneses
Institute of Chemical Research of Catalonia (ICIQ) Barcelona Institute of Science and Technology (BIST) Av. Països Catalans 16 Tarragona 43007 Spain
Aimara García‐Camacho
Department of Chemistry Instituto de Investigación Química de la Universidad de La Rioja (IQUR) Universidad de La Rioja Madre de Dios 53 Logroño 26006 Spain
Maria Vicent‐Morales
Institute of Chemical Research of Catalonia (ICIQ) Barcelona Institute of Science and Technology (BIST) Av. Països Catalans 16 Tarragona 43007 Spain
Jordi Benet‐Buchholz
Institute of Chemical Research of Catalonia (ICIQ) Barcelona Institute of Science and Technology (BIST) Av. Països Catalans 16 Tarragona 43007 Spain
Ignacio Funes‐Ardoiz
Department of Chemistry Instituto de Investigación Química de la Universidad de La Rioja (IQUR) Universidad de La Rioja Madre de Dios 53 Logroño 26006 Spain
Arjan W. Kleij