title: Investigation of the transition-metal- and acid-catalyzed reactions of beta-(N-tosyl)amino diazo carbonyl compounds.
abstract: A series of beta-(N-tosyl)amino diazo carbonyl compounds have been prepared by nucleophilic condensation of N-tosylimines with acyldiazomethanes. The diazo decomposition of these diazo carbonyl compounds under various catalytic conditions, including Rh(II) carboxylates, Cu(I) and Cu(II) complexes, PhCO(2)Ag/Et(3)N, TsOH, and SnCl(2).2H(2)O, has been investigated. It was found that, in most cases, the diazo decomposition gave preferentially 1,2-aryl migration product, but 1,2-hydride migration predominated when PhCO(2)Ag/Et(3)N was the catalytic system. Hammett correlation has been applied in the analysis of the electronic effects of 1,2-aryl migration. The factors that govern the migratory preference and the mechanistic aspects of the reaction are discussed.
authors.affiliation: Key Laboratory of Bioorganic Chemistry, Department of Chemical Biology, College of Chemistry, Peking University, Beijing 100871, China.
authors.forename: Nan
authors.initials: N
authors.lastname: Jiang
authors.forename: Zhihua
authors.initials: Z
authors.lastname: Ma
authors.forename: Zhaohui
authors.initials: Z
authors.lastname: Qu
authors.forename: Xiaoyu
authors.initials: X
authors.lastname: Xing
authors.forename: Linfeng
authors.initials: L
authors.lastname: Xie
authors.forename: Jianbo
authors.initials: J
authors.lastname: Wang