Photoredox-Catalyzed Giese Reactions: Decarboxylative Additions to Cyclic Vinylogous Amides and Esters

An effective strategy has been developed for the photoredox-catalyzed decarboxylative addition of cyclic amino acids to both vinylogous amides and esters leading to uniquely substituted heterocycles. The additions take place exclusively trans to the substituent present on the dihydropyridone ring affording stereochemical control about the new carbon-carbon bond. These reactions are operationally simplistic and afford the desired products in good to excellent isolated yields.

The Synergetic and Multifaceted Nature of Carbon-Carbon Rotation Reveals the Origin of Stability for Bulky Alkane Dimers

Designing compounds with as long carbon-carbon bond distances as possible to challenge conventional chemical wisdom is of current interest in the literature. These compounds with exceedingly long bond lengths are commonly believed to be stabilized by dispersion interactions. In this work, we build nine dimeric models with varying sizes of alkyl groups, let the carbon-carbon bond flexibly rotate, and then analyze rotation barriers with energy decomposition and information-theoretic approaches in density functional theory. Our results show that these rotations lead to extraordinarily elongated carbon-carbon bond distances and rotation barriers are synergetic and multifaceted in nature. The dominant factor contributing to the stability of the dimers with bulky alkane groups is not the dispersion force but the electrostatic interaction with steric and exchange-correlation effects playing minor yet indispensable roles.

Electrochemical Radical C(sp3)-H Arylation of Xanthenes with Electron-Rich Arenes

C(sp3)-H arylation has recently emerged as a powerful straegy for complex organic molecules synthesis through a new carbon-carbon bond formation. We herein describe an efficient electrochemical C(sp3)-H arylation of xanthenes...

Organocatalytic Difluorobenzylation of 1,2-Diketones via Mild Cleavage of Carbon−Carbon Bonds

α-aryl-α,α-Difluoroacetophenones (DFAPs) are developed as a new type of difluorobenzylation reagents that can be facilely prepared from readily available and cheap starting materials. In-situ carbon-carbon bond cleavage of electron-deficient DFAPs...

A Mechanistic Study of Syngas to Light Olefins over OXZEO Bifunctional Catalysts: Insights into the Initial Carbon-Carbon Bond Formation on the Oxide

Direct conversion of syngas into light olefins (C2=-C4=) using bifunctional catalyst composed of oxide and zeolite (OXZEO) has attracted extensive attention in both academia and industry. However, the reaction intermediates...

Development of Chiral Potassium Strong Brønsted Base Catalysts for Enantioselective Carbon–Carbon Bond-Forming Reactions

Chiral alkaline metal Brønsted bases are traditional and reliable promoters in enantioselective catalysis. Here, new chiral potassium strong base catalysts were developed for enantioselective carbon–carbon bond-forming reactions of weakly acidic...