Issue 42, 2021

Synthesis, X-ray characterization and theoretical study of all-cis 1,4:2,3:5,8:6,7-tetraepoxynaphthalenes: on the importance of the through-space α-effect

Abstract

This manuscript reports the synthesis, X-ray characterization and DFT study of a series of all-cis 1,4:2,3:5,8:6,7-tetraepoxynaphthalenes (decahydro-2,6:3,5-diepoxynaphtho[2,3-b:6,7-b′]bis(oxirene) derivatives) obtained by the tandem [4 + 2] cycloaddition between dimethyl acetylenedicarboxylate (DMAD) and three difurans as bis-dienes (the IMDAF reaction). The “pincer”-type adduct formation is controlled by using kinetic conditions. For this work, we were only interested in the synthesis of “pincer”-type adducts to study the formation self-assembled dimers that are governed by quite short C–H⋯O H-bonds. The existence of the “through-space” alpha-effect in the “pincer”-type adducts increases their ability to establish bifurcated C–H⋯O2 H-bonds in the solid state. That is, the close distance between the O-bridge atoms provokes an interesting through space lone pair⋯lone pair (LP⋯LP) interaction that increases the H-bond acceptor ability of the O-atoms. It has been analyzed using DFT calculations, molecular electrostatic potential (MEP) surfaces, quantum theory of atoms-in-molecules (QTAIM) and noncovalent interaction plot (NCIplot) index computational tools. This is the second study of the literature where “alpha-effect” hydrogen bonds (AEHBs) are described and studied. The novelty of the present work resides in the exhaustive epoxidation of the double bonds in the resulting “pincer”-type adducts that increases the number of possible H-bond acceptors in the target vicinal tetra-epoxynaphthalenes. The X-ray analyses of the three synthesized tetra-epoxides reveal that the AEHBs are predominant in the solid phase.

Graphical abstract: Synthesis, X-ray characterization and theoretical study of all-cis 1,4:2,3:5,8:6,7-tetraepoxynaphthalenes: on the importance of the through-space α-effect

Supplementary files

Article information

Article type
Paper
Submitted
07 Mha 2021
Accepted
28 Ndz 2021
First published
29 Ndz 2021

CrystEngComm, 2021,23, 7462-7470

Synthesis, X-ray characterization and theoretical study of all-cis 1,4:2,3:5,8:6,7-tetraepoxynaphthalenes: on the importance of the through-space α-effect

A. T. Le, V. T. T. Tran, D. T. Le, R. M. Gomila, A. Frontera and F. I. Zubkov, CrystEngComm, 2021, 23, 7462 DOI: 10.1039/D1CE01040A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements