English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Tools annual

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools monthly

Global: Zendy Plus monthly

Presents the access of premium content as premium feature

Premium Content

Global: Zendy Plus annual

Global: Zendy Free Plan

The development of enantioselective annulation reactions using readily available substrates for the construction of structurally and stereochemically diverse heterocycles is a compelling topic in diversity-oriented synthesis. Herein, we report efficient catalytic asymmetric formal 1,3-dipolar (3 + 4) cycloadditions of azomethine ylides with 4-indolyl allylic carbonates for the construction of azepino[3,4,5- cd ]-indoles fused with a challenging seven-membered N-heterocycle, a frequently occurring tricyclic indole scaffold in bioactive compounds and pharmaceuticals. Through cooperative Cu/Ir-catalyzed asymmetric allylic alkylation followed by intramolecular Friedel-Crafts reaction, an array of azepino[3,4,5- cd ]-indoles were obtained in good yields with excellent diastereo-/enantioselective control. More importantly, the full stereodivergence of this transformation was established via synergistic catalysis followed by acid-promoted epimerization, and up to eight stereoisomers of the cycloadducts bearing three stereogenic centers could be predictably achieved from the same set of starting materials for the first time. Quantum mechanical computations established a plausible mechanism for the synergistic Cu/Ir catalysis to stereodivergently introduce two vicinal stereocenters whose stereochemical information is remotely delivered across the fused azepine ring to control the third chiral center. Epimerization of the last center involves protonation-enabled reversal of the thermodynamically controlled relative configuration.

chemical science

Stereodivergent synthesis of enantioenriched azepino[3,4,5-<i>cd</i>]-indoles <i>via</i> cooperative Cu/Ir-catalyzed asymmetric allylic alkylation and intramolecular Friedel–Crafts reaction

Stereodivergent synthesis of enantioenriched azepino[3,4,5-cd]-indoles via cooperative Cu/Ir-catalyzed asymmetric allylic alkylation and intramolecular Friedel–Crafts reaction