An Improved Synthesis of 3,6-Dihydro-as-indacene

Yuvaraja Dibdalli; Rodrigo Faúndez; Marcelo Preite; Elies Molins; Ivonne Chávez; Mungalimane K. Amshumali; Cesar Morales-Verdejo; Juan M. Manriquez

doi:10.1055/s-0040-1707372

Synthesis, Table of Contents

Synthesis 2021; 53(03): 569-573
DOI: 10.1055/s-0040-1707372

paper

An Improved Synthesis of 3,6-Dihydro-as-indacene

Yuvaraja Dibdalli

^aDepartment of Chemistry/Industrial Chemistry, Vijayanagara Sri Krishnadevaraya University, Vinayakanagara, Cantonment, Ballari, 583105, Karnataka, India Email: amshumali.m@gmail.com

^bDepartamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile Email: ichavez@uc.cl

,

Rodrigo Faúndez

^bDepartamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile Email: ichavez@uc.cl

,

Marcelo Preite∗

^cDepartamento de Química Orgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile Email: mpreite@uc.cl

,

Elies Molins∗

^dInstituto de Ciencia de los Materiales de Barcelona (ICMAB-CSIC), Campus UAB 08193, Bellaterra, Catalunya, Spain Email: elies.molins@icmab.es

,

Ivonne Chávez∗

^bDepartamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile Email: ichavez@uc.cl

,

Mungalimane K. Amshumali∗

^aDepartment of Chemistry/Industrial Chemistry, Vijayanagara Sri Krishnadevaraya University, Vinayakanagara, Cantonment, Ballari, 583105, Karnataka, India Email: amshumali.m@gmail.com

,

Cesar Morales-Verdejo∗

^eUniversidad Bernardo O’Higgins, Centro Integrativo de Biología y Química Aplicada (CIBQA), General Gana 1702, Santiago, Chile Email: cesar.morales@ubo.cl

,

Juan M. Manriquez

^bDepartamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile Email: ichavez@uc.cl

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Abstract

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Abstract

This contribution describes an updated synthetic route to 3,6-dihydro-as-indacene along with full characterization of all intermediates. The title compound is prepared by Mannich condensation of 2-methylfuran with formaldehyde and dimethylamine hydrochloride, quaternization of the resulting amine with methyl iodide, and conversion into the ammonium hydroxide salt by treatment with silver oxide in water. Subsequent Hoffmann elimination and [6,6]-cycloaddition through pyrolysis produces a furanocyclophane, which after photooxidation, intramolecular cycloaddition, and dehydration with sodium carbonate affords 2,3,6,7-tetrahydro-1,8-dione-as-indacene. Reduction of this diketone gives a mixture of alcohols, which after dehydration under slightly basic or acidic conditions produces 3,6-dihydro-as-indacene. The structure is confirmed by X-ray diffraction, and all intermediates are characterized by means of ¹H and ¹³C NMR spectroscopy.

Key words

as-indacene - [6,6]-cycloaddition - polycyclic bridged ligand - bimetallic ligand - Mannich condensation - Hoffmann elimination

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References

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