title: Unsymmetrical Aryl(2,4,6-trimethoxyphenyl)iodonium Salts: One-Pot Synthesis, Scope, Stability, and Synthetic Studies.
abstract: Diaryliodonium salts have recently attracted significant attention as metal-free-arylation reagents in organic synthesis, and efficient access to these salts is critical for advancement of their use in reaction discovery and development. The trimethoxybenzene-derived auxiliary is a promising component of unsymmetrical variants, yet access remains limited. Here, a one-pot synthesis of aryl(2,4,6-trimethoxyphenyl)iodonium salts from aryl iodides, m-CPBA, p-toluenesulfonic acid, and trimethoxybenzene is described. Optimization of the reaction conditions for this one-pot synthesis was enabled by the method of multivariate analysis. The reaction is fast (<1 h), provides a high yield of product (>85% average), and has broad substrate scope (>25 examples) including elaborate aryl iodides. The utility of these reagents is demonstrated in moderate to high yielding arylation reactions with C-, N-, O-, and S-nucleophiles including the synthesis of a liquid crystal molecule.
authors.affiliation: Department of Chemistry, Portland State University , Portland, Oregon 97201, United States.
authors.forename: Thomas L
authors.initials: TL
authors.lastname: Seidl
authors.affiliation: Department of Chemistry, Portland State University , Portland, Oregon 97201, United States.
authors.forename: Sunil K
authors.initials: SK
authors.lastname: Sundalam
authors.affiliation: Department of Chemistry, Portland State University , Portland, Oregon 97201, United States.
authors.forename: Brennen
authors.initials: B
authors.lastname: McCullough
authors.affiliation: Department of Chemistry, Portland State University , Portland, Oregon 97201, United States.
authors.forename: David R
authors.initials: DR
authors.lastname: Stuart
mesh_terms: D001557:Benzenesulfonates / Q000737:chemistry; D002384:Catalysis; D002723:Chlorobenzoates / Q000737:chemistry; D007202:Indicators and Reagents / Q000737:chemistry; D008670:Metals / Q000737:chemistry*; D015394:Molecular Structure; D009861:Onium Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D012492:Salts / Q000737:chemistry*
chemical_list: D001557:Benzenesulfonates; D002723:Chlorobenzoates; D007202:Indicators and Reagents; D008670:Metals; D009861:Onium Compounds; D012492:Salts; C000433:3-chloroperbenzoic acid; C029501:4-toluenesulfonic acid