HDA cycloadditions of 1-diethoxyphosphonyl-1,3-butadiene with nitroso heterodienophiles: A computational investigation
(2010) Journal of Molecular Structure: THEOCHEM — Vol. 959, n° 1-3, p. 49-54 (2010)
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- Abstract
- The hetero Diets-Alder (HDA) reactions of 1-diethoxyphosphony1-1,3-butadiene with various nitroso dienophiles have been studied at the B3LYP/6-31G** level. Structural, energetic and electronic properties are discussed. These cycloadditions with nitroso dienophiles are characterized by a total proximal regioselectivity and an endo selectivity. The influence of the nitroso substitution on the activation barrier and the regiochemistry of the reaction is presented. The analysis of the chemical rearrangement along the intrinsic reaction pathway (IRC), based on bond order and on natural bond orbital (NBO) calculations, emphasizes the polar nature of these cycloadditions. Despite the early and the cyclic nature of the corresponding transition states, a two-center interaction governs this mechanism: these cycloadditions are Polar Diets-Alder reactions (P-DA). (C) 2010 Elsevier B.V. All rights reserved.
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University of Liège Ctr Ingn Proteines
Citations
Monbaliu, J.-C., Dive, G., Marchand-Brynaert, J., & Peeters, D. (2010). HDA cycloadditions of 1-diethoxyphosphonyl-1,3-butadiene with nitroso heterodienophiles: A computational investigation. Journal of Molecular Structure: THEOCHEM, 959(1-3), 49-54. https://doi.org/10.1016/j.theochem.2010.08.004 (Original work published 2010)