Transition-Metal-Free Coupling Annulation of Arynes with Ketones and Alkynoates: Assembly of Functionalized Naphthalenes

Abstract

A transition-metal-free coupling annulation reaction of arynes, ketones, and alkynoates has been demonstrated. Using this formal [2 + 2 + 2] cycloaddition reaction, a wide variety of naphthalene derivatives were conveniently constructed in one pot with high efficiency. In addition, this novel and valid annulation has been successfully applied to the synthesis of 1-phenanthrenol derivatives.

Transition-Metal-Free Benzannulation of Tricarbonyl Derivatives with Arynes: Access to 1,3-Dinaphthol Precursors for the Synthesis of Rhodamine Dye Analogues

“…Further, Huang and co-workers reported the synthesis of polysubstituted naphthols and naphthalenes using a multicomponent reaction between arynes, β-keto sulfones, and Michael-type acceptors . In 2016, Wu and co-workers reported the synthesis of polyfunctional naphthalene derivatives using an aryne–alkyne–ketone coupling annulation reaction . Treatment of arynes with diketo compounds is found to be the alternate strategy to construct the naphthalene system.…”

“…14 In 2016, Wu and co-workers reported the synthesis of polyfunctional naphthalene derivatives using an aryne− alkyne−ketone coupling annulation reaction. 15 Treatment of arynes with diketo compounds is found to be the alternate strategy to construct the naphthalene system. With this strategy, the research group of Stoltz and co-workers reported the synthesis of naphthoquinones via a one-pot aryne acylalkylation/condensation employing arynes with diketo compounds (Scheme 1, eq 1).…”

Direct Assembly of Polysubstituted Naphthalenes via a Tandem Reaction of Benzynes and α-Cyano-β-methylenones

“…11 Recently, Wu, Shu, and co-workers reported a formal [2+2+2] cycloaddition of benzynes, ketones, and alkynoates, which provided a novel method for the synthesis of functionalized naphthalenes (Scheme 1c). 12 Subsequently, the same group further developed a tandem σ-bond insertion/benzannulation reaction of benzynes to give two classes of polysubstituted naphthalenes. 13 Very recently, Mukherjee and co-workers reported an impressive Diels− Alder reaction of benzynes and glycal-derived dienes to construct meta-disubstituted naphthalenes with a chiral side chain (Scheme 1d).…”

“…In 2012, Biju and co-workers reported an interesting Diels–Alder reaction of 1,2-benzoquinones and benzynes to produce dioxobenzobicyclooctadienes, which can be further transformed to naphthalenes via irradiation at 254 nm (Scheme b) . Recently, Wu, Shu, and co-workers reported a formal [2+2+2] cycloaddition of benzynes, ketones, and alkynoates, which provided a novel method for the synthesis of functionalized naphthalenes (Scheme c) . Subsequently, the same group further developed a tandem σ-bond insertion/benzannulation reaction of benzynes to give two classes of polysubstituted naphthalenes .…”

Coumarin to Isocoumarin: One-Pot Synthesis of 3-Substituted Isocoumarins from 4-Hydroxycoumarins and Benzyne Precursors

“…On the other hand, arynes have been successfully used as versatile reactive intermediates for the synthesis of various synthetic compounds and natural products . Recently, these reactive intermediates have been extensively used for the atom-economic synthesis of valuable products as they avoid transition metals and harsh reaction conditions . Kobayashi and his group have used arynes as coupling partners for the synthesis of 3-substituted isocoumarins .…”