Nitrile oxide 1,3-dipolar cycloaddition to arylsulfonyl- and dialkylaminoallenes have been investigated within the framework of the Kohn-Sham density functional theory (DFT) at the B3LYP/6-31G(d,p) level. The hitherto-unexplained experimental behavior of sulfonylallenes was rationalized by transition-state calculations which enabled a semiquantitative treatment of the cycloaddition site- and regioselectivity. The reliability of DFT computations was further established by predicting the complete selectivity of the nitrile oxide cycloaddition to dialkylaminoallenes according to previous experimental findings.

Site- and Regioselectivity of Nitrile Oxide-Allene Cycloadditions : DFT-Based Semiquantitative Predictions / G. Molteni, A. Ponti. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - 82:19(2017 Oct 06), pp. 10710-10714. [10.1021/acs.joc.7b01866]

Site- and Regioselectivity of Nitrile Oxide-Allene Cycloadditions : DFT-Based Semiquantitative Predictions

G. Molteni
Primo
;
A. Ponti
Ultimo
2017

Abstract

Nitrile oxide 1,3-dipolar cycloaddition to arylsulfonyl- and dialkylaminoallenes have been investigated within the framework of the Kohn-Sham density functional theory (DFT) at the B3LYP/6-31G(d,p) level. The hitherto-unexplained experimental behavior of sulfonylallenes was rationalized by transition-state calculations which enabled a semiquantitative treatment of the cycloaddition site- and regioselectivity. The reliability of DFT computations was further established by predicting the complete selectivity of the nitrile oxide cycloaddition to dialkylaminoallenes according to previous experimental findings.
Settore CHIM/06 - Chimica Organica
6-ott-2017
Article (author)
File in questo prodotto:
File Dimensione Formato  
Revised.pdf

accesso aperto

Tipologia: Post-print, accepted manuscript ecc. (versione accettata dall'editore)
Dimensione 1.61 MB
Formato Adobe PDF
1.61 MB Adobe PDF Visualizza/Apri
Pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/526083
Citazioni
  • ???jsp.display-item.citation.pmc??? 1
  • Scopus 8
  • ???jsp.display-item.citation.isi??? 8
social impact