Computational Exploration of Chiral Iron Porphyrin-Catalyzed Asymmetric Hydroxylation of Ethylbenzene Where Stereoselectivity Arises from π-π Stacking Interaction
Computational Exploration of Chiral Iron Porphyrin-Catalyzed Asymmetric Hydroxylation of Ethylbenzene Where Stereoselectivity Arises from π-π Stacking Interaction
复制标题
手性铁卟啉催化乙苯不对称羟基化反应的计算探索，其中立体选择性源自α-β堆积相互作用
DOI：
10.1021/acs.joc.9b01989
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Yuan-Bin She
中科院分区：
文献类型：
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作者：
Qun-Min Wang;Xia-He Chen;Gui-Jie Li;Qi-Dong Chen;Yun-Fang Yang;Yuan-Bin She
利用密度泛函理论探讨了手性铁卟啉催化乙苯不对称羟基化立体选择性的机理和起源。氢原子的提取是决定速率和立体选择性的步骤。与实验结果非常吻合，发现 (R)-1-苯基乙醇产物的形成是最有利的途径。与导致(R)-1-苯基乙醇产物的相应过渡态相比，导致(S)-1-苯基乙醇产物的氢原子夺取过渡态不利1.7kcal/mol。对映选择性源于乙苯底物的苯基和卟啉配体的萘基之间有吸引力的 π-π 堆积相互作用。
The mechanism and origins of stereoselectivity of chiral iron porphyrin-catalyzed asymmetric hydroxylation of ethylbenzene were explored with density functional theory. The hydrogen atom abstraction is the rate- and stereoselectivity-determining step. In good agreement with experimental results, the formation of the (R)-1-phenylethanol product is found to be the most favorable pathway. The transition state of hydrogen atom abstraction which leads to the (S)-1-phenylethanol product is unfavorable by 1.7 kcal/mol compared to the corresponding transition state which leads to the (R)-1-phenylethanol product. Enantioselectivity arises from an attractive π–π stacking interaction between the phenyl group of ethylbenzene substrate and the naphthyl group of the porphyrin ligand.