Itoh Group Literature Review

Kuangbiao Liao, Solymar Negretti, Djamaladdin G. Musaev, John Bacsa & Huw M. L. Davies Emory University, Atlanta, USA. Nature 2016 , 533 , 230 http://www.nature.com/nature/journal/v533/n7602/pdf/nature17651.pdf Abstruct The laboratory synthesis of complex organic molecules relies heavily on the introduction and manipulation of functional groups, such as carbon–oxygen or carbon–halogen bonds; carbon–hydrogen bonds are far less reactive and harder to functionalize selectively. The idea of C–H functionalization, in which C–H bonds are modified at will instead of the functional groups, represents a paradigm shift in the standard logic of organic synthesis. For this approach to be generally useful, effective strategies for site-selective C–H functionalization need to be developed. The most practical solutions to the site-selectivity problem rely on either intramolecular reactions4 or the use of directing groups within the substrate. A challenging, but potenti...

A Stable Coordination Complex of Rh(IV) in an N,O-Donor Environment Shashi B. Sinha,† Dimitar Y. Shopov,† Liam S. Sharninghausen,† David J. Vinyard, Brandon Q. Mercado, Gary W. Brudvig,* and Robert H. Crabtree* Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06520, United States DOI: 10.1021/jacs.5b12148 ABSTRACT We describe facial and meridional isomers of [RhIII(pyalk)3], as well as meridional [RhIV(pyalk)3]+ {pyalk =2-(2-pyridyl)-2-propanoate}, the first coordination complex in an N,O-donor environment to show a clean, reversible RhIII/IV redox couple and to have a stable Rh(IV) form, which we characterize by EPR and UV−visible spectroscopy as well as X-ray crystallography. The unprecedented stability of the Rh(IV) species is ascribed to the exceptional donor strength of the ligands, their oxidation resistance, and the meridional coordination geometry.