77903-60-7Relevant academic research and scientific papers
A General Organocatalytic System for Electron Donor-Acceptor Complex Photoactivation and Its Use in Radical Processes
De Pedro Beato, Eduardo,Melchiorre, Paolo,Spinnato, Davide,Zhou, Wei
supporting information, p. 12304 - 12314 (2021/08/20)
We report herein a modular class of organic catalysts that, acting as donors, can readily form photoactive electron donor-acceptor (EDA) complexes with a variety of radical precursors. Excitation with visible light generates open-shell intermediates under mild conditions, including nonstabilized carbon radicals and nitrogen-centered radicals. The modular nature of the commercially available xanthogenate and dithiocarbamate anion organocatalysts offers a versatile EDA complex catalytic platform for developing mechanistically distinct radical reactions, encompassing redox-neutral and net-reductive processes. Mechanistic investigations, by means of quantum yield determination, established that a closed catalytic cycle is operational for all of the developed radical processes, highlighting the ability of the organic catalysts to turn over and iteratively drive every catalytic cycle. We also demonstrate how the catalysts' stability and the method's high functional group tolerance could be advantageous for the direct radical functionalization of abundant functional groups, including aliphatic carboxylic acids and amines, and for applications in the late-stage elaboration of biorelevant compounds and enantioselective radical catalysis.
Tandem chain extension-iodomethylation reactions: formation of α-functionalized γ-keto carbonyls
Pu, Qinglin,Wilson, Emerald,Zercher, Charles K.
, p. 8045 - 8051 (2008/12/21)
Sequential exposure of a zinc-organometallic intermediate, generated through a zinc carbenoid-mediated chain extension reaction of a β-keto carbonyl, to trimethylsilylchloride and iodine provided regioselective formation of an α-iodomethyl-γ-keto carbonyl. The iodomethyl functionality can be further manipulated to provide side chains that are potential mimics of α-amino acid side chains.
Ring Opening Reactions of Methyl 2-Siloxycyclopropanecarboxylates to Oxoalkanoic Acid Derivatives
Kunkel, Elisabeth,Reichelt, Ingrid,Reissig, Hans-Ulrich
, p. 802 - 819 (2007/10/02)
A great variety of methyl 2-(trialkylsiloxy)cyclopropanecarboxylates C1 - C31 are cleaved under very mild conditions and with excellent yields providing 4-oxoalkanoic esters D1 - D31 which are important synthetic building blocks.Even sensible esters with formyl, vinyl ketone, or trimethylsiloxy functions can be prepared.Corresponding to the regioselective synthesis of C isomeric pairs of D can deliberately be constructed.In the presence of an electrophile alkylating ring opening delivers 4-oxoalkanoates substituted in position 2, however, the degree of alkylation does not exceed 60percent.Several other cleavage variations allow syntheses of other 4-oxoalkanoic acid derivatives in effective one-pot procedures.
