TY - JOUR

T1 - 2-Azidoazirines suitable for click chemistry: synthesis of 1-(2H-azirin-2-yl)-1H-1,2,3-triazoles

AU - Golubev, A.A.

AU - Simdianov, I.V.

AU - Smetanin, I.A.

AU - Agafonova, A.V.

AU - Rostovskii, N.V.

AU - Khlebnikov, A.F.

AU - Novikov, M.S.

N1 - Export Date: 01 November 2025; Cited By: 1; Correspondence Address: M.S. Novikov; St. Petersburg State University, Institute of Chemistry, Petersburg, 7/9 Universitetskaya nab., St., 199034, Russian Federation; email: m.novikov@spbu.ru; CODEN: NJCHE

PY - 2024/11/11

Y1 - 2024/11/11

N2 - 2-Azidoazirines, sufficiently stable to be isolated in good yields, were synthesized by the cascade SN2'-SN2' substitution of bromine in methyl 2-bromo-2H-azirine-2-carboxylates using sodium azide in acetonitrile. According to the DFT calculations, the first step, Br/N3 exchange, is rate-determining and occurs in a concerted manner, while the subsequent N3/N3 exchange is a stepwise process. An alternative method using the TMSN3/Et3N/CH2Cl2 system permits the isolation in pure form of only 2-azidoazirines having ortho-substituted aryl substituent at C3, although it is more efficient in a one-pot synthesis of 1-(azirin-2-yl)-1,2,3-triazoles from the bromoazirines via the “cascade SN2'-SN2' substitution/CuAAC reaction” sequence. The protocol has a broad scope for both azirines and alkynes and provides good product yields. The described CuAAC reaction of 2-azidoazirines represents the first example of a copper(I)-catalyzed reaction of azirines that occurs with the preservation of the azirine ring.

AB - 2-Azidoazirines, sufficiently stable to be isolated in good yields, were synthesized by the cascade SN2'-SN2' substitution of bromine in methyl 2-bromo-2H-azirine-2-carboxylates using sodium azide in acetonitrile. According to the DFT calculations, the first step, Br/N3 exchange, is rate-determining and occurs in a concerted manner, while the subsequent N3/N3 exchange is a stepwise process. An alternative method using the TMSN3/Et3N/CH2Cl2 system permits the isolation in pure form of only 2-azidoazirines having ortho-substituted aryl substituent at C3, although it is more efficient in a one-pot synthesis of 1-(azirin-2-yl)-1,2,3-triazoles from the bromoazirines via the “cascade SN2'-SN2' substitution/CuAAC reaction” sequence. The protocol has a broad scope for both azirines and alkynes and provides good product yields. The described CuAAC reaction of 2-azidoazirines represents the first example of a copper(I)-catalyzed reaction of azirines that occurs with the preservation of the azirine ring.

KW - Bromine compounds

KW - Catalysis

KW - Substitution reactions

KW - Synthesis (chemical)

KW - 2H-Azirines

KW - Aryl substituents

KW - Catalyzed reactions

KW - Click chemistry

KW - DFT calculation

KW - One-pot synthesis

KW - Product yields

KW - Reaction sequences

KW - Sodium azide

KW - Synthesised

KW - Carboxylation

KW - 1,2,3 triazole derivative

KW - ascorbic acid

KW - azirine derivative

KW - nucleophile

KW - phenylacetylene

KW - Article

KW - catalyst

KW - chemical bond

KW - click chemistry

KW - column chromatography

KW - controlled study

KW - cross coupling reaction

KW - crystallization

KW - decomposition

KW - density functional theory

KW - electrophilicity

KW - isomer

KW - nucleophilicity

KW - one pot synthesis

KW - proton nuclear magnetic resonance

KW - room temperature

KW - substitution reaction

KW - Suzuki reaction

KW - synthesis

UR - https://www.mendeley.com/catalogue/3d98f5c5-f2f0-3a09-8a0d-9ee7d16d3cda/

U2 - 10.1039/d4nj03517h

DO - 10.1039/d4nj03517h

M3 - статья

VL - 48

SP - 19957

EP - 19962

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 47

ER -