Direct bromocarboxylation of arynes using allyl bromides and carbon dioxide

Abstract

An unprecedented multicomponent reaction involving arynes, allyl bromides, and CO2 has been developed to construct various allyl o-bromobenzoate scaffolds.

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

“…Moreover, Jiang and co-workers discovered an aryne MCR with allyl bromides 8-138 and CO 2 and obtained ortho -brominated aryl esters 8-139 in moderate to high yields (Scheme ). Depending on the electronic nature of the allyl bromides, they proposed two possible mechanisms. For those substrates containing electron-rich or electron-neutral groups (path a), an allylic cation 8-140 and bromide anion might be generated, the latter of which undergoes a sequential nucleophilic addition to aryne and then to CO 2 by the generated aryl anion.…”

“…Moreover, Jiang and co-workers discovered an aryne MCR with allyl bromides 8-138 and CO 2 and obtained orthobrominated aryl esters 8-139 in moderate to high yields (Scheme 148). 618 Depending on the electronic nature of the In 2010, Miyabe and co-workers first discovered that oquinone methide 8-145 could be trapped by organozinc reagents (Scheme 150a). 620,621 Subsequently, the same group developed an unprecedented MCR of arynes, DMF, and active methylenes from 1,3-diketones or β-keto esters (Scheme 150b).…”

Multicomponent Reaction of Phosphines, Benzynes, and CO2: Facile Synthesis of Stable Zwitterionic Phosphonium Inner Salts

“…Based on the pioneering studies of the three-component coupling reaction involving benzynes and CO 2 , − two plausible reaction mechanisms were proposed, as depicted in Scheme . For path a , the fluoride-induced 1,2-elimination of 2-(trimethylsilyl)­aryl triflate results in the in situ generation of benzyne.…”

Base-mediated carboxylation of C-nucleophiles with CO2

“…29). 68 Cinnamyl bromide containing electron-donating or neutral groups would ionize to generate cinnamyl cation and Br − , which react with benzyne, CO 2 , and phenylallyl cations to provide…”