Manipulating Micellar Environments for Enhancing Transition Metal-Catalyzed Cross-Couplings in Water at Room Temperature

• Published in: Journal of organic chemistry 2011-06, Vol.76 (12), p.5061-5073
• Main Authors: Lipshutz, Bruce H, Ghorai, Subir, Leong, Wendy Wen Yi, Taft, Benjamin R, Krogstad, Daniel V
• Format: Article
• Language: English
• Subjects: Alkenes - chemistry; Catalysis; Catalysts: preparations and properties; Chemistry; Colloidal state and disperse state; Exact sciences and technology; General and physical chemistry; Kinetics and mechanisms; Micelles; Micelles. Thin films; Microscopy, Electron, Transmission; Molecular Structure; Organic chemistry; Palladium - chemistry; Reactivity and mechanisms; Temperature; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Water - chemistry
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo200746y

The remarkable effects of added salts on the properties of aqueous micelles derived from the amphiphile PTS are described. Most notably, Heck reactions run in the presence of NaCl lead to couplings on aryl bromides in water at room temperature. Olefin cross- and ring-closing metathesis reactions run in the presence of small amounts of pH-lowering KHSO4 are also accelerated, another phenomenon that does not apply to typical processes in organic media. These salt effects allow, in general, for synthetically valuable C–C bond-forming processes to be conducted under environmentally benign conditions. Recycling of the surfactant is also demonstrated.