A unified framework for understanding the electronic nature of alkyl substituents is presented, resolving the contradiction between spectroscopic data and reactivity patterns typically found in organic chemistry textbooks. This framework is based on the distinct interactions of alkyl groups with σ frameworks and π systems. When attached to an sp3-hybridized atom, as in alkanes, amines, and ethers, the alkyl group acts as an inductive electron-withdrawing substituent (relative to hydrogen). This behavior reflects the greater electronegativity of carbon than hydrogen, as evidenced by NMR chemical shifts and dipole moments. The stability trends observed for aliphatic carbanions and free radicals (ethyl < isopropyl < tert-butyl in both cases) are due to this electron-withdrawing character. The acidity trend of alcohols in aqueous mixtures (methanol > ethanol > 2-propanol > tert-butanol) correlates with the decreasing permittivities of the pure alcohols. Apparent electron-donating effects inferred from Gibbs free energy acidities of ammonium ions and substituted acetic acids arise from entropic artifacts caused by hydrophobic effects. When the alkyl group is bonded to an sp2-hybridized atom, as in alkenes, arenes, carbonyl compounds, carboxylic acids, amides, heterocycles, and carbocations, or to an sp-hybridized atom, as in alkynes, concurrent hyperconjugative electron donation occurs, which overcomes the inductive electron-withdrawing effect in the tert-butyl cation. This work calls for revising textbooks to emphasize both electronic effects and to replace the misinterpreted reactivity examples with spectroscopically validated models, thereby providing a consistent framework essential for educating students and training AI systems in chemistry.

We report eCarbonyls, a scalable, metal-free electrochemical oxidation of alcohols that mimics key features of the classical Swern reaction while avoiding its reliance on cryogenic conditions and haza...

Electrochemical update to a classic reaction trades cryogenic conditions for room temperature, to selectively convert primary and secondary alcohols into aldehydes and ketones

The growing pressures of climate change, population growth, and resource scarcity have underscored the urgency of transitioning toward sustainable food systems. This chapter explores the transformativ...

Oxidative catalytic depolymerization of polystyrene (PS) can produce benzoic acid, but the annual consumption of benzoic acid is ~40 times lower than PS, so benzoic acid should be converted to higher-...

Supervisors who invest in positive mentoring relationships with their PhD candidates also reap the benefits for their own research.

Metal-organic frameworks were the next big thing in chemistry when they were invented more than three decades ago. Now, these intriguing materials are becoming commercial tools for capturing carbon dioxide and harvesting water from the air.

A robust and scalable process for the production of 8-aminooctanoic acid has been developed. Starting from commercially available azelaic acid, the target compound was obtained in four steps in a 62% ...