Novel and Convenient Synthesis of 2,7-Dialkyl-1,8-dihydro-as-indacenes­

Rodrigo Faúndez; Francisco Castillo; Marcelo Preite; Eduardo Schott; Ximena Zarate; Juan Manuel Manriquez; Elies Molins; Cesar Morales-Verdejo; Ivonne Chávez

doi:10.1055/s-0037-1610631

Synthesis, Table of Contents

Synthesis 2019; 51(02): 441-449
DOI: 10.1055/s-0037-1610631

paper

Novel and Convenient Synthesis of 2,7-Dialkyl-1,8-dihydro-as-indacenes

Rodrigo Faúndez

^aDepartamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile

,

Francisco Castillo

^aDepartamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile

,

Marcelo Preite

^bDepartamento de Química Orgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile

,

Eduardo Schott

^aDepartamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile

,

Ximena Zarate

^cInstituto de Ciencias Químicas Aplicadas, Facultad de Ingeniería, Universidad Autónoma de Chile, Av. Pedro de Valdivia 425, Santiago, Chile

,

Juan Manuel Manriquez

^aDepartamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile

,

Elies Molins

^dInstituto de Ciencia de los Materiales de Barcelona (ICMAB-CSIC), Campus UAB 08193, Bellaterra, Catalunya, Spain

,

Cesar Morales-Verdejo*

^eCentro de Nanotecnología Aplicada (CNAP), Facultad de Ciencias, Universidad Mayor, 5750 Camino la Pirámide, Huechuraba, Santiago, Chile Email: cesar.morales@umayor.cl Email: ichavez@uc.cl

,

Ivonne Chávez*

^aDepartamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile

› Author Affiliations

Abstract

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Abstract

A novel and convenient synthetic route towards dialkyl as-indacenes was achieved by alkylation of malonic esters with o-xylylene dibromide, to give the corresponding tetraester, and related diacid. The alkyl groups on the central benzene ring induce intramolecular, regiospecific cycloeliminations leading selectively to the diketones, the precursors of the corresponding 1,8-dihydro-as-indacenes. The structure of the 2,7-dimethyl-1,8-dihydro-as-indacene was determined by X-ray diffraction. The compound 2,7-diethyl-1,8-dihydro-as-indacene was characterized by means of ¹H NMR, ¹³C NMR, FT-IR, UV/Vis measurements, electrochemistry, and elemental analysis. On the other hand, quantum chemical computations based on DFT methods were carried out to get insight into the molecular and electronic structures of the studied ligands. TDDFT approach was employed to calculate the vertical excitations and characterize the nature the UV/Vis absorption bands present in the experiments showing a very good agreement between experimental and calculated values. Finally, the reactivity of the compounds was assessed using the chemical potential (μ), chemical hardness (η), and electrophilicity (ω). Also, the electron-donating (ω^–), electron-accepting (ω⁺), and the net electrophilicity powers (ω^±) indexes were studied.

Key words

regiospecific cycloeliminations - polycyclic bridge ligands - as-indacene -

Full Text

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Supplementary Material

Supporting Information

Novel and Convenient Synthesis of 2,7-Dialkyl-1,8-dihydro-as-indacenes­

Novel and Convenient Synthesis of 2,7-Dialkyl-1,8-dihydro-as-indacenes