He, Zhi-Tao published the artcileTrimethylphosphate as a Methylating Agent for Cross Coupling: A Slow-Release Mechanism for the Methylation of Arylboronic Esters, COA of Formula: C13H17BCl2O2, the publication is Journal of the American Chemical Society (2018), 140(49), 17197-17202, database is CAplus and MEDLINE.
Tri-Me phosphate acted as an effective source of Me groups; in the presence of CuI, and LiI, (MeO)3P(:O) underwent chemoselective coupling with arylpinacolboronates mediated by LiOt-Bu in 1,3-dimethylimidazolidin-2-one (DMI) to yield methylarenes in higher yields than related coupling reactions using either Me iodide or Me tosylate. The methylation reaction was used in tandem with iridium-catalyzed regioselective borylation with bis(pinacolato)diboron to provide a one-pot methylation reaction for arenes, and for trideuteromethylation of arylpinacoboronates using tris(trideuteromethyl) phosphate. The chemoselectivity of the reaction was tested using additives possessing various functional groups (robustness screen); unprotected amines, alcs., and amides and terminal alkynes were not tolerated. The methylation of 1-naphthylpinacolboronate was demonstrated on a 200 mmol scale. The kinetics of the methylation and its dependence on Li+ and I– ions was determined and a mechanism suggested. Me iodide is released slowly upon reaction of tri-Me phosphate with iodide; the low concentration of MeI enables selective reaction with arylcopper intermediates generated from the arylboronate rather than with other nucleophiles, while binding of tert-butoxide to the pinacolboronate reactants inhibits reaction of MeI with tert-butoxide.
Journal of the American Chemical Society published new progress about 942069-73-0. 942069-73-0 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Boronic acid and ester,Benzene,Boronate Esters,Boronic Acids,Boronic acid and ester, name is 2-(3,5-Dichloro-4-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and the molecular formula is C13H17BCl2O2, COA of Formula: C13H17BCl2O2.
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