Radical Hydroarylation of Functionalized Olefins and Mechanistic Investigation of Photocatalytic Pyridyl Radical Reactions
- 24 October 2018
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 140 (45), 15525-15534
- https://doi.org/10.1021/jacs.8b10238
Abstract
We report the photoredox alkylation of halopyridines using functionalized alkene and alkyne building blocks. Selective single-electron reduction of the halogenated pyridines provides the corresponding heteroaryl radicals, which undergo anti-Markovnikov addition to the alkene substrates. The system is shown to be mild and tolerant of a variety of alkene and alkyne subtypes. A combination of computational and experimental studies support a mechanism involving proton-coupled electron transfer followed by medium-dependent alkene addition and rapid hydrogen atom transfer mediated by a polarity-reversal catalyst.Keywords
Funding Information
- Division of Chemistry (CHE-1531620)
- National Institute of General Medical Sciences (R01 GM129495)
This publication has 77 references indexed in Scilit:
- Visible‐Light Photoredox Catalysis in FlowAngewandte Chemie-International Edition, 2012
- A General Solution for the 2‐Pyridyl ProblemAngewandte Chemie-International Edition, 2012
- Continuous‐Flow Synthesis of the Anti‐Malaria Drug ArtemisininAngewandte Chemie-International Edition, 2012
- Ring-Closing Metathesis Reactions on Azinium Salts: Straightforward Access to Quinolizinium Cations and Their Dihydro DerivativesThe Journal of Organic Chemistry, 2009
- Fluorinated Alcohols: A New Medium for Selective and Clean ReactionSynlett, 2003
- Laser Flash Photolysis Kinetic Studies of Enol Ether Radical Cations. Rate Constants for Heterolysis of α-Methoxy-β-phosphatoxyalkyl Radicals and for Cyclizations of Enol Ether Radical CationsJournal of the American Chemical Society, 2002
- Donor–acceptor and polarity parameters for hydrogen bonding solventsJournal of the Chemical Society, Perkin Transactions 2, 1997
- Role of Environmental Factors in the Dynamics of Intramolecular Dissociative Electron Transfer. Effect of Solvation and Ion-Pairing on Cleavage Rates of Anion RadicalsJournal of the American Chemical Society, 1995
- Solvent structural effects on proton dissociationJournal of the American Chemical Society, 1990
- Polarography of heterocyclic aromatic compounds. XIII. Polarographic fission of carbon-halogen bonds in monohalogenopyridinesCollection of Czechoslovak Chemical Communications, 1962