Shielding Effect of Micelle for Highly Effective and Selective Monofluorination of Indoles in Water

Abstract

on the occasion of his 67th birthday Highly selective directm onofluorinationo fi ndolesa nd arenes was developed through an approacht hat allows site-specific solubility of substrate and fluorine source in the micelle. This approachw as highly selectivef or ab road range of substrates with excellent functional group tolerance. Differences in binding constant and solubility of indoles and arenes in the micelle allowed the fine-tuning of selectivity.C ontrol experiments suggested ar adicalp athway and provided insighti nto the role of micelles of the environmentally benigna mphiphile PS-750-M. Dynamicl ight scattering experiments stronglyi ndicated the site-specific solubility of the substrate and fluorine source.T he methodology was successfully adapted to gram scale, and the E-factore stablished from ar ecycle study indicated that the process is environmentally responsible and sustainable.

Water as the reaction medium in organic chemistry: from our worst enemy to our best friend

“…The sulfone group was embedded within the lipophilic tail such that when MC-1 is dissolved in water, it forms micelles containing more “polar” (typically) non-polar inner cores that accommodate amino acid/peptide partners. 61 Similarly, PS-750-M 62 ( Fig. 15 , right) imitates amide solvents ( e.g.…”

“…As with most surfactants, designer surfactants ( e.g. , TPGS-750-M, 35 Nok, 66 PTS, 67 PS-750-M 62 ) have a propensity to foam, from either reactions that require gases or those which generate gas. This phenomenon can be problematic, requiring special attention and planning, such as providing extra headspace above a reaction mixture.…”

Metal–Micelle Cooperativity: Phosphine Ligand-Free Ultrasmall Palladium(II) Nanoparticles for Oxidative Mizoroki–Heck-type Couplings in Water at Room Temperature

“… 7 , 12 − 15 For example, micellar catalysis, a significant enabler of chemistry in water, has been applied to many diverse classes of organic chemistry reactions, often with improved reactivity and/or selectivity compared to their organic solvent enabled counterparts. 16 − 18 …”

Surfactant Micelles Enable Metal‐Free Spirocyclization of Keto‐Ynamides and Access to Aza‐Spiro Scaffolds in Aqueous Media

“…Metal‐catalyzed reactions carried out in micellar systems have been extensively studied . In the recent years, the scope of reactions conducted in micellar systems has significantly broadened with, for example, the aerobic oxidation of aryl alkynes the nucleophilic aromatic substitution, the sulfonylation of polyfluoroarenes and the monofluorination of indoles . The use of micellar systems in the above‐mentioned examples also limits the recourse to transition metal catalysts.…”