The Role of Acetylides in Dual Gold Catalysis: A Mechanistic Investigation of the Selectivity Difference in the Naphthalene Synthesis from Diynes

Abstract

AbstractUnder the conditions of dual activation catalysis with oxygen nucleophiles, β‐substituted naphthalenes were obtained from 1,2‐diethinyl arenes. Mechanistic studies, which include isotope labeling experiments, support that dual activation leads to β‐substituted naphthalenes, whereas α‐naphthalenes are formed by π activation only, and no gold acetylide or dual activation is involved in the formation of the α‐substituted products. Additional experiments on substrates that led to dibenzopentalenes support these mechanistic insights.