کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5416496 | 1506886 | 2010 | 6 صفحه PDF | دانلود رایگان |
The hetero Diels-Alder (HDA) reactions of 1-diethoxyphosphonyl-1,3-butadiene with various nitroso dienophiles have been studied at the B3LYP/6-31Gââ 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 Diels-Alder reactions (P-DA).
Journal: Journal of Molecular Structure: THEOCHEM - Volume 959, Issues 1â3, 15 November 2010, Pages 49-54