Mechanism and reactivity of rhodium-catalyzed intermolecular [5 ＋ 1 ] cycloaddition of 3-acyloxy-l,4-enyne （ACE） and CO： A computational study

The first theoretical study on the mechanism of [RhCl（CO）2]2-catalyzed [5 ＋ 1] cycloadditions of 3- acyloxy-1,4-enyne （ACE） and CO has been performed using density functional theory （DFT） calculations. The effect of ester on reactivity of this reaction has been investigated. The computational result...

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Bibliographic Details
Published in:中国化学快报：英文版 2015 (6), p.730-734
Main Author: Xiao-Na Ke Casi M. Schienebeck Chen-Chen Zhou Xiu-Fang Xu Wei-Ping Tang
Format: Article
Language:English
Subjects:
ACE
催化循环
分子间
反应性
烯炔
计算结果
酰氧基
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Summary:The first theoretical study on the mechanism of [RhCl（CO）2]2-catalyzed [5 ＋ 1] cycloadditions of 3- acyloxy-1,4-enyne （ACE） and CO has been performed using density functional theory （DFT） calculations. The effect of ester on reactivity of this reaction has been investigated. The computational results have revealed that the preferred catalytic cycle involves the sequential steps of 1,2-acyloxy migration, CO insertion, reductive elimination to form ketene intermediate, 6π-electroncyclization, and aromatization to afford the resorcinol product. The 1,2-acyloxy migration is found to be the rate-determining step of the catalytic cycle. The electron-rich p-dimethylaminobenzoate substrate promotes 1,2-acyloxy migration and significantly increases the reactivity by stabilizing the positive charge building up in the oxocyclic transition state.
ISSN:1001-8417
1878-5964