Ipso-Nitration of Calix[6]azacryptands: Intriguing Effect of the Small Rim Capping Pattern on the Large Rim Substitution Selectivity

作者:Lejeune Manuel; Picron Jean Francois; Mattiuzzi Alice; Lascaux Angelique; De Cesco Stephane; Brugnara Andrea; Thiabaud Gregory; Darbost Ulrich; Coquiere David; Colasson Benoit; Reinaud Olivia*; Jabin Ivan
来源:Journal of Organic Chemistry, 2012, 77(8): 3838-3845.
DOI:10.1021/jo300179h

摘要

The ipso-nitration of calix[6]arene-based molecular receptors is a important synthetic pathway for the elaboration of more sophisticated systems. This reaction has been studied for a variety of capped calixarenes, and a general trend for the regioselective nitration of three aromatic units out of six in moderate to high yield has been observed. This selectivity is, in part, attributed to the electronic connection between the protonated cap at the small rim and the reactive sites at the large rim. In addition, this work highlights the fact that subtle conformational properties can drastically influence the outcome of this reaction.

  • 出版日期2012-4-20