Water opens the door to organolithiums and Grignard reagents: exploring and comparing the reactivity of highly polar organometallic compounds in unconventional reaction media towards the synthesis of tetrahydrofurans

http://pubs.rsc.org/en/Content/ArticleLanding/2015/SC/C5SC03436A?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FSC+%28RSC+-+Chem.+Sci.+latest+articles%29#!divAbstract




Water opens the door to organolithiums and Grignard reagents: exploring and comparing the reactivity of highly polar organometallic compounds in unconventional reaction media towards the synthesis of tetrahydrofurans
Luciana Cicco, Stefania Sblendorio, Rosmara Mansueto, Filippo Maria Perna, Antonio Salomone, Saverio Florio and Vito Capriati

Chem. Sci., 2015, Accepted Manuscript
DOI: 10.1039/C5SC03436A
Received 11 Sep 2015, Accepted 02 Nov 2015
First published online 03 Nov 2015


It has always been a firm conviction of the scientific community that the employment of both anhydrous conditions and water-free reaction media are required for the successful handling of organometallic compounds with highly polarised metal–carbon bonds. Herein, we describe that, under heterogeneous conditions, Grignard and organolithium reagents can smoothly undergo nucleophilic additions to γ-chloroketones, on the way to 2,2-disubstituted tetrahydrofurans, “on water”, competitively with protonolysis, under batch condition, at room temperature and under air. The reactivity of the above organometallic reagents has also been investigated in anhydrous conventional organic solvents and in bio-based eutectic and low melting mixtures for comparison. The scope and limitations of this kind of reaction are discussed.