Exploring the in situ Utilization of Cyclic Imine Intermediates Generated by Isocyanoacetate Cycloaddition: Convergent Assembly of cis‐3a,8a‐Hexahydropyrrolo[2,3‐b]indole Scaffolds

Abstract

Under copper(I) or silver(I)/base cocatalysis conditions, transient 2H-pyrroline intermediates generated by the cycloaddition of isocyanoacetates and olefins can be in situ subjected to further transformations. A strategically novel, convergent, mild, efficient, general and atom-economic access to cis-3a,8a-hexahydropyrroloA C H T U N G T R E N N U N G [2,3-b]indoles, which are core scaffolds in many biologically important natural products, has been developed based on this concept.

Selective Electrocatalytic Oxidation of Sorbitol to Fructose and Sorbose

“…In an our previous communication, we have reported that cis ‐3a,8a‐hexahydropyrrolo[2,3‐ b ]indoles (HPIs), which are core scaffolds embedded in a large array of biologically active natural products,1 can be convergently assembled by a strategically novel, mild and atom‐economic domino reaction of isocyanoacetates and 2‐(2‐amidophenyl)acrylates 2. In spite of the fact that this Cu(I)‐ or Ag(II)‐catalyzed reaction has many advantages such as (i) the starting materials are easily available, (ii) several chiral centers including the characteristic C‐3a quaternary center can be installed in a single step, (iii) and a broad spectrum of functionalities can be tolerated, the lack of stereocontrol and thus formation of only racemic products still hampers its application.…”

Recent Advances in the Chemistry of Isocyanides with Activated Methylene Group

“…They used o-amino-substituted styrenes as substrates in the domino generation and in situ capture of these cyclic imine intermediates in cycloaddition, leading to the assembly of substituted indoles 14 (Scheme 6). [15] Scheme 6. Reaction of o-amino-substituted styrenes with isocyanoacetates.…”

Assembly of Enantioenriched cis‐3a,8a‐Hexahydropyrrolo[2,3‐b]indole Scaffolds by Silver(I)‐Catalyzed Asymmetric Domino Reaction of Isocyanoacetates in the Presence of Cinchona‐Derived Chiral Phosphorus Ligands

“…[2] In spite of the fact that this Cu(I)-or Ag(II)-catalyzedr eactionh as many advantages such as (i)t he starting materials are easily available,( ii)s everal chiral centers including the characteristic C-3a quaternary center can be installed in as ingle step, (iii)a nd abroad spectrumo ff unctionalities can be tolerated, the lack of stereocontrola nd thus formationo fo nly racemic productss till hampers its application. Therefore,t he development of an enantioselective version of this domino reactionf or the assembly of enantioenrichedH PIs is of high demandand deservesinvestigation.…”