Programmable Deoxychlorination/Aromatization of 1-Tetralones to Access Multisubstituted 1-Chloronaphthalenes via an Interrupted Vilsmeier–Haack Reaction

An unprecedented programmable sequential orthogonal deoxychlorination/aromatization of various tetralones was successfully developed for the straightforward construction of valuable multisubstituted 1-chloronaphthalenes via an interrupted Vilsmeier-Haack reaction. High efficiency, excellent site selectivity, as well as good functional group compatibility were achieved under noble-metal-free inexpensive conditions. Aiming to realize precision chemistry goal, several artificially controllable sequences were further rationally designed to access a series of highly functionalized useful 1-chloronaphthalene derivatives, which were prepared costly by previously reported methods. More importantly, this one-pot reaction could be scaled up to a 50 mmol scale without any evident erosion in efficacy and selectivity under standard conditions, demonstrating the practical applicability of this newly developed methodology. A plausible mechanism was also proposed to clarify the experimental outcomes.