钌催化氧三环烯烃异构化为1,2 -萘氧化物的DFT研究

IF 2.7 3区化学 Q2 CHEMISTRY, ORGANIC

European Journal of Organic Chemistry Pub Date : 2025-06-12 DOI:10.1002/ejoc.202500192

Austin Pounder , Noah King , William Tam

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引用次数: 0

摘要

利用密度泛函理论（DFT）研究了钌催化C1取代的不对称氧苯并甲氧二烯（OBDs）异构化的机理和区域选择性。本研究阐明了一个三步催化循环：氧化加成、η - 1 - to - η - 3 -烯丙基异构化和还原消除。自由能谱的分析表明氧化加成是速率决定步骤，也是区域选择性的主要贡献者。DFT计算预测，缺乏电子的obd倾向于生成1,2 -萘氧化物，而富有电子的obd倾向于生成1 -萘酚产物，这与实验结果一致。

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Ruthenium‐Catalyzed Isomerization of Oxabicyclic Alkenes to 1,2‐Naphthalene Oxides: A Density Functional Theory Study

The mechanism and regioselectivity of ruthenium‐catalyzed isomerization of C1‐substituted, unsymmetrical oxabenzonorbornadienes (OBDs) are investigated using density functional theory (DFT). This study elucidates a three‐step catalytic cycle: oxidative addition, η¹‐ to η³‐allyl isomerization, and reductive elimination. Analysis of the free energy profile identifies oxidative addition as the rate‐determining step and as the primary contributor to regioselectivity. DFT calculations predict that electron‐deficient OBDs preferentially yield 1,2‐naphthalene oxide, while electron‐rich OBDs favor the formation of 1‐naphthol products, in agreement with experimental findings.

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来源期刊

European Journal of Organic Chemistry 化学-有机化学

CiteScore

5.40

自引率

3.60%

发文量

752

审稿时长

1 months

期刊介绍： The European Journal of Organic Chemistry (2019 ISI Impact Factor 2.889) publishes Full Papers, Communications, and Minireviews from the entire spectrum of synthetic organic, bioorganic and physical-organic chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form two leading journals, the European Journal of Organic Chemistry and the European Journal of Inorganic Chemistry: Liebigs Annalen Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry.