外消旋化
分子内力
化学
苯胺
戒指(化学)
单独一对
2-降冰片酰阳离子
氢键
吡啶
立体化学
结晶学
药物化学
分子
有机化学
作者
Sagar D. Vaidya,Beeta S Heydari,Sean T. Toenjes,Jeffrey L. Gustafson
标识
DOI:10.1021/acs.joc.2c00451
摘要
Diarylamines possess two potentially atropisomeric C–N axes; however, there are few examples of atropisomerically stable diarylamines in the literature, as the contiguous axes can allow for low energy racemization pathways via concerted bond rotations. Herein, we describe highly atropisomerically stable diarylamines that possess barriers to racemization of 30–36 kcal/mol, corresponding to half-lives to racemization on the decade to century time scale at room temperature. Investigation of the factors that led to the high stereochemical stability suggests that increased conjugation of the aniline lone pair of electrons into a more electron-deficient aryl ring, coupled with intramolecular hydrogen-bonding, locked the corresponding axis into a defined planar conformation, disfavoring the lower energy racemization pathways.
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