Next Article in Journal
Essential Oil Extraction, Chemical Analysis and Anti-Candida Activity of Calamintha nepeta (L.) Savi subsp. glandulosa (Req.) Ball—New Approaches
Next Article in Special Issue
Theoretical Reactivity Study of Indol-4-Ones and Their Correlation with Antifungal Activity
Previous Article in Journal
Backstabbing P-gp: Side-Chain Cleaved Ecdysteroid 2,3-Dioxolanes Hyper-Sensitize MDR Cancer Cells to Doxorubicin without Efflux Inhibition
Previous Article in Special Issue
A Computational Study of Structure and Reactivity of N-Substitued-4-Piperidones Curcumin Analogues and Their Radical Anions
Article Menu
Issue 2 (February) cover image

Export Article

Open AccessArticle
Molecules 2017, 22(2), 202; doi:10.3390/molecules22020202

The Nitrilimine–Alkene Cycloaddition Regioselectivity Rationalized by Density Functional Theory Reactivity Indices

1
Dipartimento di Chimica, Università degli Studi di Milano, via C. Golgi 19, 20133 Milano, Italy
2
Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche, via C. Golgi 19, 20133 Milano, Italy
*
Author to whom correspondence should be addressed.
Received: 8 November 2016 / Accepted: 19 January 2017 / Published: 26 January 2017
View Full-Text   |   Download PDF [1030 KB, uploaded 3 February 2017]   |  

Abstract

Conventional frontier molecular orbital theory is not able to satisfactorily explain the regioselectivity outcome of the nitrilimine–alkene cycloaddition. We considered that conceptual density functional theory (DFT) could be an effective theoretical framework to rationalize the regioselectivity of the title reaction. Several nitrilimine–alkene cycloadditions were analyzed, for which we could find regioselectivity data in the literature. We computed DFT reactivity indices at the B3LYP/6-311G(2d,p)//B3LYP/6-31G(d,p) and employed the grand potential stabilization criterion to calculate the preferred regioisomer. Experimental and calculated regioselectivity agree in the vast majority of cases. It was concluded that predominance of a single regioisomer can be obtained by maximizing (i) the chemical potential difference between nitrilimine and alkene and (ii) the local softness difference between the reactive atomic sites within each reactant. Such maximization can be achieved by carefully selecting the substituents on both reactants. View Full-Text
Keywords: 1,3-dipolar cycloaddition; nitrilimine; alkene; regioselectivity; conceptual density functional theory; reactivity indices; softness 1,3-dipolar cycloaddition; nitrilimine; alkene; regioselectivity; conceptual density functional theory; reactivity indices; softness
Figures

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

Molteni, G.; Ponti, A. The Nitrilimine–Alkene Cycloaddition Regioselectivity Rationalized by Density Functional Theory Reactivity Indices. Molecules 2017, 22, 202.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]

Molecules EISSN 1420-3049 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top