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

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

Yuvaraja Dibdalli
a  Department of Chemistry/Industrial Chemistry, Vijayanagara Sri Krishnadevaraya University, Vinayakanagara, Cantonment, Ballari, 583105, Karnataka, India   Email: [email protected]
b  Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile   Email: [email protected]
,
Rodrigo Faúndez
b  Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile   Email: [email protected]
,
Marcelo Preite
c  Departamento de Química Orgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile   Email: [email protected]
,
Elies Molins
d  Instituto de Ciencia de los Materiales de Barcelona (ICMAB-CSIC), Campus UAB 08193, Bellaterra, Catalunya, Spain   Email: [email protected]
,
Ivonne Chávez
b  Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile   Email: [email protected]
,
Mungalimane K. Amshumali
a  Department of Chemistry/Industrial Chemistry, Vijayanagara Sri Krishnadevaraya University, Vinayakanagara, Cantonment, Ballari, 583105, Karnataka, India   Email: [email protected]
,
Cesar Morales-Verdejo
e  Universidad Bernardo O’Higgins, Centro Integrativo de Biología y Química Aplicada (CIBQA), General Gana 1702, Santiago, Chile   Email: [email protected]
,
Juan M. Manriquez
b  Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile   Email: [email protected]
› Author Affiliations
The authors are grateful for the financial support from Fondo Nacional de Desarrollo Científico y Tecnológico, Chile (FONDECYT) (Grants 1161297, EQM120021, EQM130032, EQM150102), the Pontificia Universidad Católica de Chile (PUC) (Grant 3913-541-81), the Scheduled Tribes Welfare Department, Government of Karnataka, India for a student fellowship (Y.D.) to pursue a research stay at the Pontificia Universidad Católica de Chile. E.M. (ICMAB) acknowledges the Severo Ochoa Program, Ministerio de Economía y Competitividad (MINECO) (SEV-2015-0496).


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.

Supporting Information



Publication History

Received: 11 June 2020

Accepted after revision: 11 August 2020

Publication Date:
02 September 2020 (online)

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