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Enantioselective reductive cross-couplings to forge C(sp)-C(sp) bonds by merging electrochemistry with nickel catalysis.

Nat Commun

January 2025

State Key Laboratory of Organometallic Chemistry, Shanghai of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, PR China.

Motivated by the inherent benefits of synergistically combining electrochemical methodologies with nickel catalysis, we present here a Ni-catalyzed enantioselective electroreductive cross-coupling of benzyl chlorides with aryl halides, yielding chiral 1,1-diaryl compounds with good to excellent enantioselectivity. This catalytic reaction can not only be applied to aryl chlorides/bromides, which are challenging to access by other means, but also to benzyl chlorides containing silicon groups. Additionally, the absence of a sacrificial anode lays a foundation for scalability.

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Photooxidation and Cleavage of Ethynylated 9,10-Dimethoxyanthracenes with Acid-Labile Ether Bonds.

J Org Chem

January 2025

Department of Chemistry, Tufts University, 62 Talbot Avenue, Medford, Massachusetts, 02155, United States.

This paper describes a series of 12 9,10-dimethoxyanthracene derivatives functionalized with a range of electronically diverse ethynyl substituents at the 2 and 6 positions, aimed at tuning their optoelectronic properties and reactivity with singlet oxygen (O). Optical spectroscopy, cyclic voltammetry, and density functional theory calculations reveal that the ethynyl groups decrease the HOMO-LUMO gaps in these acenes. Notably, bis(dimethylanilineethynyl) substituents increase the wavelength of absorbance onset by over 60 nm compared to 9,10-dimethoxyanthracene (DMA).

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Strained spiro-heterocycles (SSH) have gained significant attention within the medicinal chemistry community as promising (sp3)-rich bioisosteres for their aromatic and non-spirocyclic counterparts. We herein report access to an unprecedented spiro-heterocycle - 1,5-dioxaspiro[2.3]hexane.

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Escalating energy demands have often ignited ground-breaking innovations in the current era of electrochemical energy storage systems. Supercapacitors (SCs) have emerged as frontrunners in this regard owing to their exclusive features such ultra-high cyclic stability, power density, and ability to be derived from sustainable sources. Despite their promising attributes, they typically fail in terms of energy density, which poses a significant hindrance to their widespread commercialization.

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Fast-scan cyclic voltammetry (FSCV) is a widely used electrochemical technique to measure the phasic response of neurotransmitters in the brain. It has the advantage of reducing tissue damage to the brain due to the use of carbon fiber microelectrodes as well as having a high temporal resolution (10 Hz) sufficient to monitor neurotransmitter release in vivo. During the FSCV experiment, the surface of the carbon fiber microelectrode is inevitably changed by the fouling effect.

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