Theoretical study on cycloaddition of singlet dichlorocarbene with formaldehyde, acetaldehyde and benzaldehyde and subsequent rearrangement reactions

L. Peng; Q. S. Li; W. H. Fang; C. J. Fu; J. Zhang

doi:10.1016/j.cplett.2003.10.053

Theoretical study on cycloaddition of singlet dichlorocarbene with formaldehyde, acetaldehyde and benzaldehyde and subsequent rearrangement reactions

L. Peng, Q. S. Li, W. H. Fang^*, C. J. Fu, J. Zhang

^*Corresponding author for this work

Beijing Normal University

Research output: Contribution to journal › Article › peer-review

7 Citations (Scopus)

Abstract

Cycloaddition reactions of the singlet CCl₂ carbene with H ₂CO, CH₃CHO and C₆H₅CHO and the subsequent rearrangement processes have been investigated with density functional theory. It was found that the interaction between the σ orbital of CCl₂ and the C=O π* orbital plays an important role in the cycloaddition reactions. The addition reaction of CCl₂ with H₂CO proceeds very easily, which is slightly influenced by the methyl and phenyl substitutions. However, the substitutions significantly reduce the barrier to the rearrangement reactions. The interaction between solvent and solute has a little influence on the structures of the stationary points, but has a noticeable influence on the barrier heights of the rearrangement reactions.

Original language	English
Pages (from-to)	126-132
Number of pages	7
Journal	Chemical Physics Letters
Volume	382
Issue number	1-2
DOIs	https://doi.org/10.1016/j.cplett.2003.10.053
Publication status	Published - 28 Nov 2003
Externally published	Yes

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10.1016/j.cplett.2003.10.053

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title = "Theoretical study on cycloaddition of singlet dichlorocarbene with formaldehyde, acetaldehyde and benzaldehyde and subsequent rearrangement reactions",

abstract = "Cycloaddition reactions of the singlet CCl2 carbene with H 2CO, CH3CHO and C6H5CHO and the subsequent rearrangement processes have been investigated with density functional theory. It was found that the interaction between the σ orbital of CCl2 and the C=O π* orbital plays an important role in the cycloaddition reactions. The addition reaction of CCl2 with H2CO proceeds very easily, which is slightly influenced by the methyl and phenyl substitutions. However, the substitutions significantly reduce the barrier to the rearrangement reactions. The interaction between solvent and solute has a little influence on the structures of the stationary points, but has a noticeable influence on the barrier heights of the rearrangement reactions.",

author = "L. Peng and Li, {Q. S.} and Fang, {W. H.} and Fu, {C. J.} and J. Zhang",

year = "2003",

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doi = "10.1016/j.cplett.2003.10.053",

language = "English",

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journal = "Chemical Physics Letters",

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T1 - Theoretical study on cycloaddition of singlet dichlorocarbene with formaldehyde, acetaldehyde and benzaldehyde and subsequent rearrangement reactions

AU - Peng, L.

AU - Li, Q. S.

AU - Fang, W. H.

AU - Fu, C. J.

AU - Zhang, J.

PY - 2003/11/28

Y1 - 2003/11/28

N2 - Cycloaddition reactions of the singlet CCl2 carbene with H 2CO, CH3CHO and C6H5CHO and the subsequent rearrangement processes have been investigated with density functional theory. It was found that the interaction between the σ orbital of CCl2 and the C=O π* orbital plays an important role in the cycloaddition reactions. The addition reaction of CCl2 with H2CO proceeds very easily, which is slightly influenced by the methyl and phenyl substitutions. However, the substitutions significantly reduce the barrier to the rearrangement reactions. The interaction between solvent and solute has a little influence on the structures of the stationary points, but has a noticeable influence on the barrier heights of the rearrangement reactions.

AB - Cycloaddition reactions of the singlet CCl2 carbene with H 2CO, CH3CHO and C6H5CHO and the subsequent rearrangement processes have been investigated with density functional theory. It was found that the interaction between the σ orbital of CCl2 and the C=O π* orbital plays an important role in the cycloaddition reactions. The addition reaction of CCl2 with H2CO proceeds very easily, which is slightly influenced by the methyl and phenyl substitutions. However, the substitutions significantly reduce the barrier to the rearrangement reactions. The interaction between solvent and solute has a little influence on the structures of the stationary points, but has a noticeable influence on the barrier heights of the rearrangement reactions.

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DO - 10.1016/j.cplett.2003.10.053

M3 - Article

AN - SCOPUS:0344851680

SN - 0009-2614

VL - 382

SP - 126

EP - 132

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 1-2

ER -

Theoretical study on cycloaddition of singlet dichlorocarbene with formaldehyde, acetaldehyde and benzaldehyde and subsequent rearrangement reactions

Abstract

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