Publications by authors named "Gregory S Sauer"
Article Synopsis
- The study presents a new, efficient electrochemical method for creating C-O and C-N bonds in compounds from simple alkenes, highlighting its milder conditions compared to traditional approaches.
- Through mechanistic investigations, researchers identified a unique reaction pathway involving the formation of azidyl radicals facilitated by an electrochemically generated oxoammonium ion, differing from previous methods.
- The findings indicate that the reversible dissociation of a TEMPO-azide complex is a critical step in the reaction, suggesting potential broader applications for aminoxyl radical chemistry in synthesis.
Article Synopsis
- The protocol outlines an electrochemical method for synthesizing 1,2-diazides from alkenes, highlighting the importance of these compounds in synthetic chemistry and biological applications.
- The process involves generating azidyl radicals from sodium azide and using a manganese catalyst, with minimal waste and enhanced control compared to traditional methods.
- Additionally, the resulting 1,2-diazides can be efficiently reduced to 1,2-diamines, and the protocol emphasizes sustainability and versatility through the use of various accessible materials and experimental setups.
Article Synopsis
- The study describes a method for creating chlorotrifluoromethylated pyrrolidines using a specific electrochemical process called anodically coupled electrolysis.
- This process involves two parallel oxidation reactions that effectively combine to form a beneficial pathway.
- The use of readily available chemicals and a manganese catalyst, with the addition of a chelating ligand, helps ensure precise control over the product's stereochemistry during synthesis.
The emergence of new catalytic strategies that cleverly adopt concepts and techniques frequently used in areas such as photochemistry and electrochemistry has yielded a myriad of new organic reactions that would be challenging to achieve using orthodox methods. Herein, we discuss the strategic use of anodically coupled electrolysis, an electrochemical process that combines two parallel oxidative events, as a complementary approach to existing methods for redox organic transformations. Specifically, we demonstrate anodically coupled electrolysis in the regio- and chemoselective chlorotrifluoromethylation of alkenes.
View Article and Find Full Text PDFElectrocatalytic Radical Dichlorination of Alkenes with Nucleophilic Chlorine Sources.
J Am Chem Soc
November 2017
We report a Mn-catalyzed electrochemical dichlorination of alkenes with MgCl as the chlorine source. This method provides operationally simple, sustainable, and efficient access to a variety of vicinally dichlorinated compounds. In particular, alkenes with oxidatively labile functional groups, such as alcohols, aldehydes, sulfides, and amines, were transformed into the desired vicinal dichlorides with high chemoselectivity.
View Article and Find Full Text PDFVicinal diamines are a common structural motif in bioactive natural products, therapeutic agents, and molecular catalysts, motivating the continuing development of efficient, selective, and sustainable technologies for their preparation. We report an operationally simple and environmentally friendly protocol that converts alkenes and sodium azide-both readily available feedstocks-to 1,2-diazides. Powered by electricity and catalyzed by Earth-abundant manganese, this transformation proceeds under mild conditions and exhibits exceptional substrate generality and functional group compatibility.
View Article and Find Full Text PDFExperimental (13)C kinetic isotope effects have been used to interrogate the rate-limiting step of the Michael addition of glycinate imines to benzyl acrylate catalyzed by a chiral 2,3-bis(dicyclohexylamino) cyclopropenimine catalyst. The reaction is found to proceed via rate-limiting carbon-carbon bond formation. The origins of enantioselectivity and a key noncovalent CH···O interaction responsible for transition state organization are identified on the basis of density functional theory calculations and probed using experimental labeling studies.
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