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A DFT study on the mechanisms for the cycloaddition reactions between 1−aza-2-azoniaallene cations and acetylenes

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Abstract

The mechanisms of cycloaddition reactions between 1-aza-2-azoniaallene cations 1 and acetylenes 2 have been investigated using the global electrophilicity and nucleophilicity of the corresponding reactants as global reactivity indexes defined within the conceptual density functional theory. The reactivity and regioselectivity of these reactions were predicted by analysis of the energies, geometries, and electronic nature of the transition state structures. The theoretical results revealed that the reaction features a tandem process: an ionic 1,3-dipolar cycloaddition to produce the cycloadducts 3 H-pyrazolium salts 3 followed by a [1,2]-shift affording the thermodynamically more stable adducts 4 or 5. The mechanism of the cycloaddition reactions can be described as an asynchronous concerted pathway with reverse electron demand. The model reaction has also been investigated at the QCISD/6-31++G(d,p) and CCSD(T)/6-31++G(d,p)//B3LYP/6-31++G(d,p) levels as well as by the DFT. The polarizable continuum model, at the B3LYP/6-31++G(d,p) level of theory, was used to study solvent effects on all the studied reactions. In solvent dichloromethane, all the initial cycloadducts 3 were obtained via direct ionic process as the result of the solvent effect. The consecutive [1,2]-shift reaction, in which intermediates 3 are rearranged to the five-membered heterocycles 4/5, is proved to be a kinetically controlled reaction, and the regioselectivity can be modulated by varying the migrant. The LOL function and RDG function based on localized electron analysis were used to analysis the covalent bond and noncovalent interactions in order to unravel the mechanism of the title reactions.

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Abbreviations

B3LYP:

Becke-3-parameter-Lee-Yang-Parr

QCISD:

Quadratic configuration interaction using single and double substitutions

CCSD(T):

Coupled cluster calculations with single and double excitations and a perturbative estimate of triple contributions

DFT:

Density functional theory

PCM:

Polarized continuum model

IRC:

Intrinsic reaction coordinate

NBO:

Natural bond orbital

LOL:

Localized orbital locator

RDG:

Reduced density gradient

AM1:

Austin model 1

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Acknowledgments

We acknowledge the assistance of other members of Professor Quan-rui Wang's group for obtaining experimental information. This work was supported by the National Natural Science Foundation of China (No. 21102019) and the Science Fund for Distinguished Young Scholars at Fudan University.

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Authors and Affiliations

  1. Department of Chemistry, Fudan University, Shanghai, 200433, People’s Republic of China

    Jing-mei Wang, Zhi-ming Li, Quan-rui Wang & Feng-gang Tao

  2. Research Centre for Analysis & Measurement, Fudan University, Shanghai, 200433, People’s Republic of China

    Jing-mei Wang

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  1. Jing-mei Wang
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  2. Zhi-ming Li
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Correspondence to Zhi-ming Li.

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Wang, Jm., Li, Zm., Wang, Qr. et al. A DFT study on the mechanisms for the cycloaddition reactions between 1−aza-2-azoniaallene cations and acetylenes. J Mol Model 19, 83–95 (2013). https://doi.org/10.1007/s00894-012-1521-1

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