HDA cycloadditions of 1-diethoxyphosphonyl-1,3-butadiene with nitroso heterodienophiles: A computational investigation

Jean-Christophe Monbaliu , Georges Dive , Jacqueline Marchand-Brynaert , Daniel Peeters
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引用次数: 6

Abstract

The hetero Diels–Alder (HDA) reactions of 1-diethoxyphosphonyl-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 Diels–Alder reactions (P-DA).

1-二氧基膦-1,3-丁二烯与亚硝基异二烯试剂的HDA环加成:计算研究
在B3LYP/6-31G * *水平上研究了1-二氧基膦-1,3-丁二烯与各种亚硝基亲二烯试剂的异diols - alder (HDA)反应。讨论了材料的结构、能量和电子性能。这些与亚硝基亲二烯试剂的环加成具有完全的近端选择性和内端选择性。介绍了亚硝基取代对反应的激活势垒和区域化学的影响。根据键序和自然键轨道(NBO)计算,沿着本征反应路径(IRC)进行化学重排分析,强调了这些环加成的极性性质。尽管相应的过渡态具有早期和循环的性质,但两中心相互作用支配着这一机制:这些循环加成是极性Diels-Alder反应(P-DA)。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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