Synlett 2023; 34(05): 437-440
DOI: 10.1055/a-1946-6578
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Special Edition Thieme Chemistry Journals Awardees 2022

Computational Investigation of the Aza-Cope Rearrangement Leading to Angularly Substituted 1-Azabicyclic Rings

Ricardo Meyrelles 
a   Institute of Organic Chemistry, University of Vienna, Währinger Straße 38, 1090 Vienna, Austria
b   Institute of Theoretical Chemistry, University of Vienna, Währinger Straße 17, 1090 Vienna, Austria
c   Vienna Doctoral School in Chemistry, University of Vienna, Währinger Straße 42, 1090 Vienna, Austria
,
Yener Fetisleam
b   Institute of Theoretical Chemistry, University of Vienna, Währinger Straße 17, 1090 Vienna, Austria
,
Boris Maryasin  ∗
a   Institute of Organic Chemistry, University of Vienna, Währinger Straße 38, 1090 Vienna, Austria
b   Institute of Theoretical Chemistry, University of Vienna, Währinger Straße 17, 1090 Vienna, Austria
› Author AffiliationsWe thank the University of Vienna for support of research programs and the Doctoral School in Chemistry for funding.
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Abstract

A computational study of the aza-Cope rearrangement leading to angularly substituted 1-azabicyclic ring systems is presented. The calculations estimate the probability of the proton transfer between reaction intermediates and protic solvents, explain the experimentally observed reaction selectivity, and suggest new potentially more efficient systems for further in vitro and in silico investigations.

Key words

aza-Cope rearrangement - DFT - reaction mechanisms - sigmatropic rearrangements - proton transfer - cis–trans selectivity

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1946-6578.
  • Supporting Information


Publication History

Received: 30 July 2022

Accepted after revision: 18 September 2022

Accepted Manuscript online:
18 September 2022

Article published online:
28 October 2022

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