Abstract
Direct amination is an extremely valuable reaction, allowing for the one-step preparation of aromatic amines. However, its mechanism was poorly studied. Here, for the first time, using quantum chemical calculations, we have shown that direct amination of arenes by hydrazoic acid follows the classical S E Ar mechanism with aminodiazonium cation H 2 N 3 + as electrophile. The peculiarity of H 2 N 3 + electronic structure has been described using our novel method for tracing the molecular orbitals. The located stationary points and transition states allowed us to define direct amination as S E Ar reaction, which rate is determined by early transition state between π- and σ-complexes. Considering the calculated reaction constant ρ and an early transition state, we placed direct amination of arenes by HN 3 somewhere in-between nitration and halogenations. Our results explain the accumulated experimental data and open a prospect for the development of the new aminating agents working in milder conditions.
| Original language | English |
|---|---|
| Pages (from-to) | 2933-2940 |
| Number of pages | 8 |
| Journal | ChemistrySelect |
| Volume | 4 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - 14 Mar 2019 |
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Keywords
- amination
- density functional theory
- electrophilic substitution
- hydrazoic acid
- tracing the molecular orbitals
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Mechanism of Direct Electrophilic Aromatic Amination : an Electrophile is Found by Quantum-Chemical Study. / Stankevich, Ksenia S.; Bondarev, Alexander A.; Lavrinenko, Anastasia K.; Filimonov, Victor D.
In: ChemistrySelect, Vol. 4, No. 10, 14.03.2019, p. 2933-2940.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Mechanism of Direct Electrophilic Aromatic Amination
T2 - an Electrophile is Found by Quantum-Chemical Study
AU - Stankevich, Ksenia S.
AU - Bondarev, Alexander A.
AU - Lavrinenko, Anastasia K.
AU - Filimonov, Victor D.
PY - 2019/3/14
Y1 - 2019/3/14
N2 - Direct amination is an extremely valuable reaction, allowing for the one-step preparation of aromatic amines. However, its mechanism was poorly studied. Here, for the first time, using quantum chemical calculations, we have shown that direct amination of arenes by hydrazoic acid follows the classical S E Ar mechanism with aminodiazonium cation H 2 N 3 + as electrophile. The peculiarity of H 2 N 3 + electronic structure has been described using our novel method for tracing the molecular orbitals. The located stationary points and transition states allowed us to define direct amination as S E Ar reaction, which rate is determined by early transition state between π- and σ-complexes. Considering the calculated reaction constant ρ and an early transition state, we placed direct amination of arenes by HN 3 somewhere in-between nitration and halogenations. Our results explain the accumulated experimental data and open a prospect for the development of the new aminating agents working in milder conditions.
AB - Direct amination is an extremely valuable reaction, allowing for the one-step preparation of aromatic amines. However, its mechanism was poorly studied. Here, for the first time, using quantum chemical calculations, we have shown that direct amination of arenes by hydrazoic acid follows the classical S E Ar mechanism with aminodiazonium cation H 2 N 3 + as electrophile. The peculiarity of H 2 N 3 + electronic structure has been described using our novel method for tracing the molecular orbitals. The located stationary points and transition states allowed us to define direct amination as S E Ar reaction, which rate is determined by early transition state between π- and σ-complexes. Considering the calculated reaction constant ρ and an early transition state, we placed direct amination of arenes by HN 3 somewhere in-between nitration and halogenations. Our results explain the accumulated experimental data and open a prospect for the development of the new aminating agents working in milder conditions.
KW - amination
KW - density functional theory
KW - electrophilic substitution
KW - hydrazoic acid
KW - tracing the molecular orbitals
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UR - http://www.scopus.com/inward/citedby.url?scp=85062939086&partnerID=8YFLogxK
U2 - 10.1002/slct.201803911
DO - 10.1002/slct.201803911
M3 - Article
AN - SCOPUS:85062939086
VL - 4
SP - 2933
EP - 2940
JO - ChemistrySelect
JF - ChemistrySelect
SN - 2365-6549
IS - 10
ER -