Vessel effects in organic chemical reactions; a century-old, overlooked phenomenon

Abstract

One of the most intriguing aspects of synthetic chemistry is the interplay of numerous dependent and independent variables en route to achieve a successful, high-yielding chemical transformation. The experienced synthetic...

Electronically Ambivalent Hydrodefluorination of Aryl‐CF3 groups enabled by Electrochemical Deep‐Reduction on a Ni Cathode

“…A modest scope of substrates was examined, demonstrating moderate to good yields of ArCFH 2 products. [54] Considering how deep the required reduction potentials are to effect this 4-electron/2-proton transformation, Figure 1D, the substitution tolerated was varied, and complex biologically relevant molecules were converted (2-34 c). Of additional interest, biaryl 34 a was better tolerated in the di-than in the mono-hydrodefluorination, which is likely due to resonance stabilization of the intermediate radical anion.…”

Enantioselective Reductive Conjugate Alkenylation of α,β-Unsaturated Ketones and Amides via Nickel Catalysis

“…The common alcohols or water were needed to hydrolyze nickel enolates and release the nickel catalyst after alkenyl addition (entries 9–11). The amounts of alcohols, typically in 1–2 equiv, were precisely controlled in order to obtain good yields of products, because the amount of adsorbed water and silanols on the surface of dry pyrex vessels is minuscule, but uncontrollable . (d) In the reaction of alkenyl bromides, addition of 1 equiv of NaBr helped to slightly increase the stereoselectivity (88 → 94% ee, entry 1 vs 12).…”

trans-Carbonylchloridobis(triethylphosphane-κP)platinum(II) tetrafluoridoborate

“…Evidently, the carbonyl oxygen atom had been extracted from the Pyrex glassware by the tetrafluoroethylene reagent. That reaction vessels are not always as inert as they are expected to be is the subject of a recent review by Nielsen & Pedersen (2022) in which formation of the title compound in this paper is one of several examples of fluorine compounds reacting with glassware.…”