Silver Hexafluoroantimonate‐Catalyzed Three‐Component [2+2+1] Cycloadditions of Allenoates, Dual Activated Olefins, and Isocyanides

Abstract

The intermolecular [2 + 2 + 1] multicomponent cycloadditions from readily available allen-A C H T U N G T R E N N U N G oates, dual activated olefins and isocyanides catalyzed by silver hexafluoroantimonate were studied. This protocol allowed the syntheses of highly functionalized five-membered carbocycles with exclusive regioselectivity and stereoselectivity in an efficient and atom-economical manner.

Isocyanide‐Based Multicomponent Reactions: Concise Synthesis of Spirocyclic Oxindoles with Molecular Complexity by Using a [1,5]‐Hydrogen Shift as the Key Step

“…In 2011, we reported the first example of a multicomponent reaction involving an isocyanide and allenoate 8a. Since then, we have spent much time in exploring the potential synthetic utility of the isocyanide‐based [2+2+1] three‐component reactions with allenoate, thus providing a quick access to the syntheses of functionalized carbocycles and natural‐product‐like N‐containing heterocycles 8b. c Mechanistically, the above‐mentioned three‐component reaction is closely related to famous phosphine‐catalyzed cycloaddition with allenoate (Scheme ).…”

Transition Metal and Inner Transition Metal Catalyzed Amide Derivatives Formation through Isocyanide Chemistry

“…Li, Jia, and co-workers reported a nucleophilic addition of isocyanides to substituted benzylidenemalonates 184 in the presence of Ag + catalyst which led to (carbamoylben-zylidene)malonates 185 (Scheme 58). 124 The Ag + catalyst behaves as a Lewis acid to promote the C-C coupling reaction.…”

Silver and gold-catalyzed multicomponent reactions

“…An interesting application of silver catalysis in the allene chemistry field has been recently proposed by Jia and co-workers [ 99 ]. The authors got inspired by the recent development of the phosphine-catalyzed [3 + 2] cycloaddition of allenoates with electron-deficient species such as olefins and imines, which involves the in situ formation of a zwitterionic intermediate from the nucleophilic addition between allenoate and phosphine.…”