The Role of Through-Bond Stereoelectronic Effects in the Reactivity of 3-Azabicyclo[3.3.1]nonanes
The Role of Through-Bond Stereoelectronic Effects in the Reactivity of 3-Azabicyclo[3.3.1]nonanes
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DOI：
10.1021/acs.joc.1c02992
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发表时间：
2022-03-04
影响因子：
3.6
通讯作者：
Tantillo，Dean J.
中科院分区：
文献类型：
--
作者：
Laconsay，Croix J.;Rho，Tyler C.;Tantillo，Dean J.
用密度泛函理论研究了3-氮杂双环[3.3.1]壬烷的超共轭/通过键共轭的立体电子效应，以解释氯乙烯（4）和乙烯基二氯乙烷酯（5）之间令人困惑的反应性差异。Risch及其同事发现这些化合物-其结构仅因一个取代基而不同-在盐酸中显示出显著不同的反应性（J. Am.化学会，1991，113，9411 - 9412）。取代基效应，非共价相互作用，自然键轨道，isodesmic反应，和水合倾向的计算分析导致一个模型的远程，通过键立体电子效应的作用是关键来解释4and 5的发散反应。
Hyperconjugation/conjugation through-bond stereoelectronic effects were studied with density functional theory in the context of 3-azabicyclo[3.3.1]nonanes to unravel puzzling differences in reactivity between a vinylogous chloride (4) and a vinylogous ester (5). These compounds─whose structures differ only by one substituent─were found to display strikingly different reactivities in hydrochloric acid by Risch and co-workers (J. Am. Chem. Soc., 1991, 113, 9411−9412). Computational analyses of substituent effects, noncovalent interactions, natural bond orbitals, isodesmic reactions, and hydration propensities lead to a model for which the role of remote, through-bond stereoelectronic effects is the key to explaining4and5’s diverging reactivity.