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Spectroscopic Characterization and Electrocyclic Ring Opening of Parent 2‐Azetine.

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Title: Spectroscopic Characterization and Electrocyclic Ring Opening of Parent 2‐Azetine.
Authors: Portela‐González, Adrián1 (AUTHOR), Kühn, Daniel1 (AUTHOR), Eckhardt, André K.1 (AUTHOR) andre.eckhardt@ruhr‐uni‐bochum.de
Source: Journal of Physical Organic Chemistry. Apr2026, Vol. 39 Issue 4, p1-7. 7p.
Subjects: Matrix isolation, Ring-opening reactions, Molecular spectroscopy, Infrared spectroscopy, Lactams, Vibrational spectra, Pyrolysis
Abstract: (N‐Boc)‐protected 2‐azetine serves as a suitable precursor for the generation of parent 2‐azetine. High‐vacuum flash pyrolysis experiments at 200°C induce the deprotection of the (N‐Boc)‐protected 2‐azetine resulting in the release of carbon dioxide and isobutene allowing the trapping of 2‐azetine in a solid argon matrix at 3 K and its spectroscopic characterization by infrared spectroscopy. The assignment is supported by isotopic labeling experiments and excellent agreement with anharmonic vibrational frequencies calculated at the B2PLYP‐D3/def2‐TZVPP level of theory. At elevated pyrolysis temperatures, 2‐azetine undergoes selective ring opening to yield 1‐azabutadiene, for which both s‐trans‐(E) and s‐trans‐(Z) conformers are observed. Computed reaction pathways and free‐energy profiles rationalize the temperature‐dependent product distribution and the observed torquoselectivity. These results provide fundamental insight into the structure, stability, and reactivity of 2‐azetine and establish matrix isolation as a powerful approach for accessing highly strained nitrogen heterocycles. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Physical Organic Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
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DbLabel: Engineering Source
An: 192311178
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
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  Data: Spectroscopic Characterization and Electrocyclic Ring Opening of Parent 2‐Azetine.
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  Data: <searchLink fieldCode="AR" term="%22Portela‐González%2C+Adrián%22">Portela‐González, Adrián</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Kühn%2C+Daniel%22">Kühn, Daniel</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Eckhardt%2C+André K%2E%22">Eckhardt, André K.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> andre.eckhardt@ruhr‐uni‐bochum.de</i>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Organic+Chemistry%22">Journal of Physical Organic Chemistry</searchLink>. Apr2026, Vol. 39 Issue 4, p1-7. 7p.
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  Data: <searchLink fieldCode="DE" term="%22Matrix+isolation%22">Matrix isolation</searchLink><br /><searchLink fieldCode="DE" term="%22Ring-opening+reactions%22">Ring-opening reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+spectroscopy%22">Molecular spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Infrared+spectroscopy%22">Infrared spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Lactams%22">Lactams</searchLink><br /><searchLink fieldCode="DE" term="%22Vibrational+spectra%22">Vibrational spectra</searchLink><br /><searchLink fieldCode="DE" term="%22Pyrolysis%22">Pyrolysis</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: (N‐Boc)‐protected 2‐azetine serves as a suitable precursor for the generation of parent 2‐azetine. High‐vacuum flash pyrolysis experiments at 200°C induce the deprotection of the (N‐Boc)‐protected 2‐azetine resulting in the release of carbon dioxide and isobutene allowing the trapping of 2‐azetine in a solid argon matrix at 3 K and its spectroscopic characterization by infrared spectroscopy. The assignment is supported by isotopic labeling experiments and excellent agreement with anharmonic vibrational frequencies calculated at the B2PLYP‐D3/def2‐TZVPP level of theory. At elevated pyrolysis temperatures, 2‐azetine undergoes selective ring opening to yield 1‐azabutadiene, for which both s‐trans‐(E) and s‐trans‐(Z) conformers are observed. Computed reaction pathways and free‐energy profiles rationalize the temperature‐dependent product distribution and the observed torquoselectivity. These results provide fundamental insight into the structure, stability, and reactivity of 2‐azetine and establish matrix isolation as a powerful approach for accessing highly strained nitrogen heterocycles. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Physical Organic Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
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    Identifiers:
      – Type: doi
        Value: 10.1002/poc.70071
    Languages:
      – Code: eng
        Text: English
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        PageCount: 7
        StartPage: 1
    Subjects:
      – SubjectFull: Matrix isolation
        Type: general
      – SubjectFull: Ring-opening reactions
        Type: general
      – SubjectFull: Molecular spectroscopy
        Type: general
      – SubjectFull: Infrared spectroscopy
        Type: general
      – SubjectFull: Lactams
        Type: general
      – SubjectFull: Vibrational spectra
        Type: general
      – SubjectFull: Pyrolysis
        Type: general
    Titles:
      – TitleFull: Spectroscopic Characterization and Electrocyclic Ring Opening of Parent 2‐Azetine.
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            NameFull: Portela‐González, Adrián
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            NameFull: Kühn, Daniel
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          Name:
            NameFull: Eckhardt, André K.
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            – D: 01
              M: 04
              Text: Apr2026
              Type: published
              Y: 2026
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              Value: 39
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              Value: 4
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            – TitleFull: Journal of Physical Organic Chemistry
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