Aryne‐Based Multicomponent Reactions

Three-Component Aminoselenation of Arynes

“…During the course of our studies on three-component coupling employing arynes, , we recently envisioned that the use of organoselenium reagents as the electrophilic third component could result in the synthesis of functionalized diaryl selenides. A series of nucleophiles can trigger aryne three-component reactions (Scheme , eq 1). , Although various electrophiles such as carbonyl compounds including CO 2 , , activated imines, and halides are known as electrophilic third components, the use of organoselenium reagents to intercept the in situ generated aryl anions in aryne three-component coupling, to the best of our knowledge, is unknown .…”

Three-Component, Diastereoselective [6 + 3] Annulation of Tropone, Imino Esters, and Arynes

“…We have recently demonstrated the generation of strained aziridinium ylide A by the reaction of arynes with N -substituted aziridines, and the formed ylide was trapped with aldehydes for the diastereoselective synthesis of 2-amino epoxides (eq 2). , Inspired by the work of Hwu and co-workers, we envisioned that the nitrogen ylide generated from the Schiff base and aryne could be intercepted with tropone in a [6 + 3] annulation reaction for convenient access to azabicyclo[4.3.1]­decadienes. This three-component coupling is likely to proceed via the initial formation of the 1,4-zwitterion B from the Schiff base and aryne, which could undergo a proton transfer to form the nitrogen ylide C , and a subsequent [6 + 3] annulation could result in the formation of the bicyclic products (eq 3).…”

An Umpolung Oxa-[2,3] Sigmatropic Rearrangement Employing Arynes for the Synthesis of Functionalized Enol Ethers

“…With the advent of a transition-metal-free procedure for the formation of arynes by the 1,2-elimination of 2-(trimethylsilyl) aryl triflates using a fluoride source (Kobayashi method), the chemistry of these electrophilic intermediates has received a resurgence of interest in the past three decades . This intermediate has been widely used in pericyclic reactions, insertion into element–element bonds, three-component coupling reactions, and various reactions catalyzed by transition metals . Additionally, numerous molecular rearrangements can proceed via aryne intermediates .…”