Showing papers by "Donna G. Blackmond published in 2014"
TL;DR: Electrochemical reactions are shown to be effective for the C-H functionalization of a number of heterocyclic substrates that are recalcitrant to conventional peroxide radical initiation conditions.
Abstract: Electrochemical reactions are shown to be effective for the C—H functionalization of a number of heterocyclic substrates that are recalcitrant to conventional peroxide radical initiation conditions. Monitoring reaction progress under electrochemical conditions provides mechanistic insight into the C—H functionalization of a series of heterocycles of interest in medicinal chemistry.
244 citations
TL;DR: This work provides support for a mechanistic concept for enamine catalysis and includes a general role for "downstream intermediates" in selectivity outcomes in organocatalysis.
Abstract: An unusual solvent-induced inversion of the sense of enantioselectivity observed in the α-selenylation of aldehydes catalyzed by a diphenylprolinol silyl ether catalyst is correlated to the presence of intermediates formed subsequent to the highly selective CSe bond-forming step in the catalytic cycle. This work provides support for a mechanistic concept for enamine catalysis and includes a general role for “downstream intermediates” in selectivity outcomes in organocatalysis.
33 citations
TL;DR: In this article, a semi-empirical population balance model is presented based on considerations of the solubility driving force, as outlined by the Gibbs-Thomson rule, and a frequency factor based on the total interfacial surface area between solid crystals and the solution phase.
Abstract: Experimental studies help to deconvolute the driving forces for crystal growth during attrition-enhanced deracemization, demonstrating an interplay between crystal size and crystal number in the emergence of homochirality. A semiempirical population balance model is presented based on considerations of the solubility driving force, as outlined by the Gibbs–Thomson rule, and a frequency factor based on the total interfacial surface area between solid crystals and the solution phase.
23 citations
TL;DR: In this paper, the conjugate addition of 2-phenylpropanal to nitro-olefins catalyzed by two different primary amine thiourea catalysts revealed the nature of the catalyst resting state.
7 citations
TL;DR: The authors reviewed chemical and physical models with a special focus on recent developments in attritionenhanced deracemization of conglomerates, a process that combines solution phase chemical interconversion of enantiomers with thermodynamic and kinetic considerations of solubility, crystal growth, and dissolution.
Abstract: The past several decades have witnessed the development of a number of different experimental approaches to help understand how the homochirality of biological molecules might have evolved in a prebiotic world. This chapter reviews chemical and physical models with a special focus on recent developments in attrition-enhanced deracemization of conglomerates, a process that combines solution phase chemical interconversion of enantiomers with thermodynamic and kinetic considerations of solubility, crystal growth, and dissolution.