The Azide-Allene Dipolar Cycloaddition: Is DFT Able to Predict Site- and Regio-Selectivity?

The Azide-Allene Dipolar Cycloaddition: Is DFT Able to Predict Site- and Regio-Selectivity?

The site- and regio-selectivity of thermal, uncatalysed 1,3-dipolar cycloadditions between arylazides and mono- or tetra-substituted allenes with different electronic features have been investigated by both conceptual (reactivity indices) and computational (M08-HX, ωB97X-D, and B3LYP) DFT approaches...

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Bibliographic Details
Main Authors: Giorgio Molteni, Alessandro Ponti
Format: Article
Language:English
Published: MDPI AG 2021-02-01
Series:Molecules
Subjects:
1,3-dipolar cycloaddition
allene
azide
M08-HX
local softness
Online Access:https://www.mdpi.com/1420-3049/26/4/928
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spelling doaj-e96b0c4326984d088deb74b43d4a36bc2021-02-11T00:00:54ZengMDPI AGMolecules1420-30492021-02-012692892810.3390/molecules26040928The Azide-Allene Dipolar Cycloaddition: Is DFT Able to Predict Site- and Regio-Selectivity?Giorgio Molteni0Alessandro Ponti1Dipartimento di Chimica, Università degli Studi di Milano, via Golgi 19, 20133 Milano, ItalyIstituto di Scienze e Tecnologie Chimiche “Giulio Natta” (SCITEC), Consiglio Nazionale delle Ricerche, via Golgi 19, 20133 Milano, ItalyThe site- and regio-selectivity of thermal, uncatalysed 1,3-dipolar cycloadditions between arylazides and mono- or tetra-substituted allenes with different electronic features have been investigated by both conceptual (reactivity indices) and computational (M08-HX, ωB97X-D, and B3LYP) DFT approaches. Both approaches show that these cycloadditions follow a nonpolar one-step mechanism. The experimental site- and regio-selectivity of arylazides towards methoxycarbonyl- and sulfonyl-allenes as well as tetramethyl- and tetrafluoro-allenes was calculated by DFT transition state calculations, achieving semiquantitative agreement to both previous and novel experimental findings. From the mechanistic standpoint, <sup>1</sup>H-NMR evidence of a methylene-1,2,3-triazoline intermediate reinforces the reliability of the computational scheme.https://www.mdpi.com/1420-3049/26/4/9281,3-dipolar cycloadditionalleneazideM08-HXlocal softness
collection DOAJ
language English
format Article
sources DOAJ
author Giorgio Molteni
Alessandro Ponti
spellingShingle Giorgio Molteni
Alessandro Ponti
The Azide-Allene Dipolar Cycloaddition: Is DFT Able to Predict Site- and Regio-Selectivity?
Molecules
1,3-dipolar cycloaddition
allene
azide
M08-HX
local softness
author_facet Giorgio Molteni
Alessandro Ponti
author_sort Giorgio Molteni
title The Azide-Allene Dipolar Cycloaddition: Is DFT Able to Predict Site- and Regio-Selectivity?
title_short The Azide-Allene Dipolar Cycloaddition: Is DFT Able to Predict Site- and Regio-Selectivity?
title_full The Azide-Allene Dipolar Cycloaddition: Is DFT Able to Predict Site- and Regio-Selectivity?
title_fullStr The Azide-Allene Dipolar Cycloaddition: Is DFT Able to Predict Site- and Regio-Selectivity?
title_full_unstemmed The Azide-Allene Dipolar Cycloaddition: Is DFT Able to Predict Site- and Regio-Selectivity?
title_sort azide-allene dipolar cycloaddition: is dft able to predict site- and regio-selectivity?
publisher MDPI AG
series Molecules
issn 1420-3049
publishDate 2021-02-01
description The site- and regio-selectivity of thermal, uncatalysed 1,3-dipolar cycloadditions between arylazides and mono- or tetra-substituted allenes with different electronic features have been investigated by both conceptual (reactivity indices) and computational (M08-HX, ωB97X-D, and B3LYP) DFT approaches. Both approaches show that these cycloadditions follow a nonpolar one-step mechanism. The experimental site- and regio-selectivity of arylazides towards methoxycarbonyl- and sulfonyl-allenes as well as tetramethyl- and tetrafluoro-allenes was calculated by DFT transition state calculations, achieving semiquantitative agreement to both previous and novel experimental findings. From the mechanistic standpoint, <sup>1</sup>H-NMR evidence of a methylene-1,2,3-triazoline intermediate reinforces the reliability of the computational scheme.
topic 1,3-dipolar cycloaddition
allene
azide
M08-HX
local softness
url https://www.mdpi.com/1420-3049/26/4/928
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