title: Palladium-catalyzed mono-N-allylation of unprotected anthranilic acids with allylic alcohols in aqueous media.
abstract: Palladium-catalyzed N-allylation of anthranilic acids 1a-j with allyl alcohol 2a in the presence of Pd(OAc)(2), sodium diphenylphosphinobenzene-3-sulfonate (TPPMS) in THF-H(2)O at room temperature gave only mono-N-allylated anthranilic acids 3a-j in good yields (70-98%). The reactions of 4-bromoanthranilic acid 1i with 2-methyl-3-buten-2-ol 2b showed complete chemoselectivity in N-allylation (neutral conditions) and C-vinylation (basic conditions). In our catalytic system, the keys to success are use of an unprotected anthranilic acid as a starting material and the presence of water in the reaction medium. The carboxyl group of anthranilic acid and water may play important roles for the smooth generation of the π-allyl palladium species by activation of the hydroxyl group of the allylic alcohol.
authors.affiliation: Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan. hidemasa.hikawa@phar.toho-u.ac.jp
authors.forename: Hidemasa
authors.initials: H
authors.lastname: Hikawa
authors.forename: Yuusaku
authors.initials: Y
authors.lastname: Yokoyama
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D002626:Chemistry, Pharmaceutical / Q000379:methods*; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D020005:Propanols / Q000737:chemistry*; D013237:Stereoisomerism; D014867:Water; D062367:ortho-Aminobenzoates / Q000737:chemistry*
chemical_list: D000498:Allyl Compounds; D020005:Propanols; D062367:ortho-Aminobenzoates; D014867:Water; C006463:allyl alcohol; D010165:Palladium