Synthesis 2020; 52(22): 3356-3373
DOI: 10.1055/s-0040-1706402
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© Georg Thieme Verlag Stuttgart · New York

One-Pot Synthesis of γ-Azidobutyronitriles and Their Intramolecular Cycloadditions

Konstantin L. Ivanov
a  Lomonosov Moscow State University, Department of Chemistry, Leninskie gory 1-3, Moscow 119991, Russian Federation   Email: ekatbud@kinet.chem.msu.ru
,
Hamidulla B. Tukhtaev
a  Lomonosov Moscow State University, Department of Chemistry, Leninskie gory 1-3, Moscow 119991, Russian Federation   Email: ekatbud@kinet.chem.msu.ru
,
Feruza O. Tukhtaeva
a  Lomonosov Moscow State University, Department of Chemistry, Leninskie gory 1-3, Moscow 119991, Russian Federation   Email: ekatbud@kinet.chem.msu.ru
,
Stanislav I. Bezzubov
b  Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskiy pr. 31, Moscow 119991, Russian Federation
,
Mikhail Ya. Melnikov
a  Lomonosov Moscow State University, Department of Chemistry, Leninskie gory 1-3, Moscow 119991, Russian Federation   Email: ekatbud@kinet.chem.msu.ru
,
Ekaterina M. Budynina
a  Lomonosov Moscow State University, Department of Chemistry, Leninskie gory 1-3, Moscow 119991, Russian Federation   Email: ekatbud@kinet.chem.msu.ru
c  Lebedev Physical Institute, Russian Academy of Sciences, Leninskiy pr. 53, Moscow 119991, Russian Federation
› Author Affiliations
Research related to the development of a one-pot synthetic approach to azidonitriles was supported by the Russian Science Foundation (19-73-00244). Research related to the development of synthetic procedures for converting azidonitriles into tetrazoles was supported by the Russian Foundation for Basic Research (18-53-41009), and by the Ministry of Innovative Development of the Republic of Uzbekistan (MRU-FA-74/2017).
Further Information

Publication History

Received: 19 May 2020

Accepted after revision: 22 June 2020

Publication Date:
04 August 2020 (online)


Abstract

Efficient gram-scale, one-pot approaches to azidocyanobutyrates and their amidated or decarboxylated derivatives have been developed, starting from commercially available aldehydes and cyanoacetates. These techniques combine (1) Knoevenagel condensation, (2) Corey–Chaykovsky cyclopropanation and (3) nucleophilic ring opening of donor-acceptor cyclopropanes with the azide ion, as well as (4) Krapcho decarboxylation or (4′) amidation. The synthetic utility of the resulting γ-azidonitriles was demonstrated by their transformation into tetrazoles via intramolecular (3+2)-cycloaddition. A condition-dependent activation effect of the α-substituent was revealed in that case. Thermally activated azide–nitrile interaction did not differentiate the presence of an α-electron-withdrawing substituent in γ-azidonitriles, whereas the Lewis acid mediated (SnCl4 or TiCl4) reaction proceeded much easier for azidocyanobutyrates. This allowed us to develop an efficient procedure for converting azidocyanobutyrates into the corresponding tetrazoles.

Supporting Information

 
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