NBO and NICS analysis of the allylic rearrangements (the Cope and 3-aza-Cope rearrangements) of hexa-1,5-diene and N-vinylprop-2-en-1-amine: A DFT study

• Authors: Ehsan Zahedi , Safa Ali-Asgari , Vahid Keley
• Languages of publication: EN

Abstracts

EN

In this work, ab initio density functional theory (DFT) calculations have been performed on the 3,3-sigmatropic rearrangements of hexa-1,5-diene (Cope) and N-vinylprop-2-en-1-amine (3-aza-Cope) in the gas phase. The barrier heights and heats of reactions calculated at the B3LYP/6-311G** level of theory were in good agreement with experimental data. Transition states optimized with B3LYP/6-311G** theory were used for calculating the nucleus independent chemical shift (NICS) and, a natural bond orbital (NBO) analysis was also performed at the same level of theory. Our results indicate that the aromaticities of the transition states are controlled by the out-of-plane component and that the chair-like transition state of the Cope rearrangement exhibits the strongest aromatic character. Analysis of donor-acceptor (bonding and anti-bonding) interactions of σ3–4 → π*1–2 suggests that the TS structure in the hexa-1,5-diene reaction (the Cope rearrangement) has more aromatic character than the N-vinylprop-2-en-1-amine reaction (the 3-aza-Cope rearrangement). The NBO results show that in the hexa-1,5-diene and N-vinylprop-2-en-1-amine rearrangements, activation energies are controlled by σ3–4 → π*1–2 and σ3–4 → π*1–2 resonance energies. [...]

Keywords

EN

Cope rearrangement; 3-Aza-Cope rearrangement; DFT; NBO; Aromaticity

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2010
• Volume: 8
• Issue: 5
• Pages: 1097-1104

Dates

published

1 - 10 - 2010

online

5 - 9 - 2010

Contributors

author

Ehsan Zahedi

• Chemistry Department, Islamic Azad University, Shahrood Branch P.O.box 36155/133, Shahrood, Iran

author

Safa Ali-Asgari

• Chemistry Department, Islamic Azad University, Shahrood Branch P.O.box 36155/133, Shahrood, Iran

author

Vahid Keley

• Chemistry Department, Shahrood University of Technology, P.O.box 316, Shahrood, Iran

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Identifiers

DOI

10.2478/s11532-010-0084-1