Premium
Copper‐Catalyzed Aerobic Oxidative CH Functionalizations: Trends and Mechanistic Insights
Author(s) -
Wendlandt Alison E.,
Suess Alison M.,
Stahl Shan S.
Publication year - 2011
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201103945
Subject(s) - catalysis , chemistry , stoichiometry , copper , electron transfer , oxidative coupling of methane , redox , photochemistry , molecule , combinatorial chemistry , inorganic chemistry , organic chemistry
The selective oxidation of CH bonds and the use of O 2 as a stoichiometric oxidant represent two prominent challenges in organic chemistry. Copper(II) is a versatile oxidant, capable of promoting a wide range of oxidative coupling reactions initiated by single‐electron transfer (SET) from electron‐rich organic molecules. Many of these reactions can be rendered catalytic in Cu by employing molecular oxygen as a stoichiometric oxidant to regenerate the active copper(II) catalyst. Meanwhile, numerous other recently reported Cu‐catalyzed CH oxidation reactions feature substrates that are electron‐deficient or appear unlikely to undergo single‐electron transfer to copper(II). In some of these cases, evidence has been obtained for the involvement of organocopper(III) intermediates in the reaction mechanism. Organometallic CH oxidation reactions of this type represent important new opportunities for the field of Cu‐catalyzed aerobic oxidations.