Synthesis of Dibenzylbutane and 9,8′-Neo-Lignans via Cyclometalation of Allylbenzene by EtAlCl<sub>2</sub> and Mg in the Presence of Zr <i>ansa</i>-Complexes

The aim of the research is the development of a one-pot method for the synthesis of lignans, natural compounds that show a wide spectrum of biological activities. For this purpose, the <i>ansa</i>-zirconocenes of various structures were tested as catalysts of allylbenzene cyclometalation...

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Bibliographic Details
Main Authors: Pavel V. Kovyazin, Pavel V. Ivchenko, Ilya E. Nifant’ev, Lyudmila V. Parfenova
Format: Article
Language:English
Published: MDPI AG 2021-11-01
Series:Chemistry Proceedings
Subjects:
Online Access:https://www.mdpi.com/2673-4583/8/1/60
Description
Summary:The aim of the research is the development of a one-pot method for the synthesis of lignans, natural compounds that show a wide spectrum of biological activities. For this purpose, the <i>ansa</i>-zirconocenes of various structures were tested as catalysts of allylbenzene cyclometalation with ethylaluminum dichloride (EtAlCl<sub>2</sub>) and Mg. The effects of the organophosphorus compounds, hexamethylphosphoramide (HMPA) and triphenylphosphine (PPh<sub>3</sub>), on the chemo- and regioselectivity of the reaction were studied. The use of <i>η</i><sup>5</sup>-indenyl or fluorenyl <i>ansa</i>-complexes with ethanediyl or dimethylsilylene bridges, as well as a biscyclopentadienyl complex with Si-bound ligands as catalysts in the presence of HMPA, yields the formation of cyclometalation products in a total yield of 70%. Cyclometalation product composition is represented by two regioisomers, 3,4-dibenzyl- and 2,4-dibenzyl-substituted alumolanes, with a ratio of (1-2):1, in which hydrolysis provides corresponding dibenzylbutane lignan and 9,8′-neo-lignan.
ISSN:2673-4583