A Base-Promoted One-Pot Asymmetric Friedel–Crafts Alkylation/Michael Addition of 4-Substituted Indoles

Robert Connon; Laura Carroll; Patrick J. Guiry

doi:10.1055/s-0039-1690241

Synthesis, Table of Contents

Synthesis 2020; 52(08): 1215-1222
DOI: 10.1055/s-0039-1690241

special topic

A Base-Promoted One-Pot Asymmetric Friedel–Crafts Alkylation/Michael Addition of 4-Substituted Indoles

Robert Connon

^aSynthesis and Solid State Pharmaceutical Center (SSPC), School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland

^bCentre for Synthesis and Chemical Biology (CSCB), School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland Email: p.guiry@ucd.ie

,

Laura Carroll

^bCentre for Synthesis and Chemical Biology (CSCB), School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland Email: p.guiry@ucd.ie

,

Patrick J. Guiry∗

^aSynthesis and Solid State Pharmaceutical Center (SSPC), School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland

^bCentre for Synthesis and Chemical Biology (CSCB), School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland Email: p.guiry@ucd.ie

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Abstract

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Dedicated with respect and admiration to Professor Mark Lautens, a good friend and brilliant chemist, on the occasion of his 60^th birthday.

Published as part of the Special Topic Domino C–H Functionalization/Cascade Catalysis

Abstract

Herein, we report a base-promoted Zn(II)–bis(oxazoline)-catalyzed one-pot Friedel–Crafts alkylation/Michael addition of 3-(indol-4-yl)acrylonitrile derivatives with trans-β-nitrostyrenes to yield the tricyclic core of the ergoline skeleton in up to 71% yield and 85% ee. During the purification of 3-(indol-4-yl)acrylonitrile, the key substrate for catalytic studies, a novel trans-cis-trans-cyclobutane derivative, thought to be formed via a [2+2] light-promoted cycloaddition, was identified by X-ray crystallographic analysis. Finally, a novel class of 4-substituted bis(indole)methane derivatives were serendipitously prepared in excellent yield by reacting 4-substituted indole derivatives with 4-nitrobenzaldehyde. One bis(indole)methane was characterized by X-ray crystallographic analysis.

Key words

enantioselective - oxazoline ligand - ergoline - indole - catalysis

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References

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