Regiochemistry of the Coupling of Aryl Radicals with Nucleophiles Derived from the Naphthyl System. Experimental and Theoretical Studies

PIERINI, A. B.; BAUMGARTNER, M. T; ROSSI, R.A.

JOURNAL OF ORGANIC CHEMISTRY

AMER CHEMICAL SOC

Lugar: Washington; Año: 1991 vol. 56 p. 580 - 580

0022-3263

e here report the photostimulated reaction of unactivated aromatic halides with ambident nucleophiles derived from the naphthyl system such as 1- and 2-naphthylamide, 2-naphthoxide, 2-11aphthalenethiolate~ and 2- naphthaleneselenate ions, by the SRNl mechanism of nucleophilic substitution. According to our experimental results, C-arylation in position 1 of the naphthyl moiety is the only reaction observed with 2-naphthoxide ions and it is favored over N-arylation with 1- and 2-naphthylamide ions. Heteroatom arylation is preferred over C-arylation with 2-naphthalenethiolate ions while it is the only observed reaction with 2-naphthaleneeelenate ions. A theoretical study was carried out to explain the regochemistry of the system. In competition experiments, 2-naphthalenethiolate ions proved to be 1.8 * 0.2 times more reactive than 2-naphthoxide ions for C-substitution toward p-anisyl radicals in liquid ammonia.