Overturning Established Chemoselectivities: Selective Reduction of Arenes over Malonates and Cyanoacetates by Photoactivated Organic Electron Donors

Citations Over TimeTop 10% of 2013 papers

Abstract

The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate-metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates.

Related Papers

• → Effect of Folin Reagent from Different Sources on Protease Determination(2013)1 cited
• STUDIES ON ANALYTICAL FUNCTIONAL GROUPS OF ORGANIC REAGENTS USED IN INORGANIC ANALYSIS——II.ON REAGENTS FOR ANTIMONOUS IONS(1956)
• Performance evaluation of stability of the total bile acid reagent with improved reagent bottles(2011)
• → ChemInform Abstract: Preparation of Fluorous Yamaguchi Reagents and Evaluation of Their Reactivity in Esterification.(2016)
• → ChemInform Abstract: Fluorinated Organocopper Reagents(2010)