Perhaloacylation of α-Carbonyl Sulfoxonium Ylides

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 2, 2025

A mild and efficient protocol for the perhaloacylation of α-carbonyl sulfoxonium ylides has been developed. The commercially available perfluoro- perchloroacid anhydrides were used as acylating agents in catalyst- additive-free reactions to access α-carbonyl-α'-perhaloacyl high yields. reaction offers a simple method prepare valuable polyfluorinated organosulfur molecules.

Language: Английский

Applying Active Learning toward Building a Generalizable Model for Ni-Photoredox Cross-Electrophile Coupling of Aryl and Alkyl Bromides

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 22, 2025

When developing machine learning models for yield prediction, the two main challenges are effectively exploring condition space and substrate space. In this article, we disclose an approach mapping Ni/photoredox-catalyzed cross-electrophile coupling of alkyl bromides aryl in a high-throughput experimentation (HTE) context. This model employs active (in particular, uncertainty querying) as strategy to rapidly construct model. Given vastness space, focused on that builds initial then uses minimal data set expand into new chemical spaces. built virtual 22,240 compounds using less than 400 points. We demonstrated can be expanded 33,312 by adding information around 24 building blocks (<100 additional reactions). Comparing learning-based one constructed randomly selected showed was significantly better at predicting which reactions will successful. A combination density function theory (DFT) difference Morgan fingerprints employed random forest Feature importance analysis indicates key DFT features related reaction mechanism (e.g., radical LUMO energy) were crucial performance predictions outside training set. anticipate combining featurization uncertainty-based querying help synthetic organic community build predictive data-efficient manner other feature large diverse scopes.

Language: Английский

Catalyst‐Free Direct Hydrocarbonation of Terminal Alkynes Toward E‐Alkene Substituted Stabilized Sulfoxonium Ylides

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: April 2, 2025

Amide and alkene moieties are frequently found in natural products privileged structures pharmaceuticals agrochemicals. Moreover, vinyl sulfoxonium ylide can be converted into a broad range of high-value compounds, thus they have been widely employed organic synthesis. However, the synthesis alkene-substituted amide-sulfoxonium ylides via intermolecular hydrocarbonation alkynes remains underexplored. This study describes development high-throughput approach to provide diverse functionalized E-alkene substituted (hetero)amide-sulfoxonium ylides. The reaction occurs under mild metal-free conditions, employing as highly effective nucleophiles, which participate Michael addition reactions with various alkynes, such esters, thioesters, ketones, amides, sulfones. low-cost, operationally simple has substrate scope, high functional group compatibility, excellent regio- stereoselectivity, making it suitable for transformation structurally complex molecules. Furthermore, obtained stabilized directly useful valuable 1,5-dicarbonyl thiabenzene 1-oxide compounds.

Language: Английский