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  • 刊名： 河北师范大学学报（自然科学版）Journal of Hebei Normal University (Natural Science)
  • 主办： 河北师范大学
  • ISSN： 1000-5854
  • CN： 13-1061/N
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AuCl3催化羟基苯炔基酮合成氧杂螺酮的理论研究

  • 贵州师范大学 化学与材料科学学院, 贵州 贵阳 550001
  • DOI： 10.11826/j.issn.1000-5854.2014.02.013

Study on the Synthesis of Unsaturated Carbonyl-oxaspiro via Gold(Ⅲ)-catalyzed Isomerization of 2-hydroxy-2-(phenylethynyl)clohexanone

摘要/Abstract

摘要：

用量子化学密度泛函理论（DFT）B3LYP方法在 6-311++G（d，p）基组的计算水平，对AuCl3催化羟基-苯炔基酮合成不饱氧杂螺酮的反应机理进行了理论研究.研究表明，该反应最优势路径包括炔基的活化、羰基氧与炔基碳亲核环化反应、螺碳的形成、双分子间的氢转移和催化剂解离等步骤.AuCl3催化作用的本质在于，Au（Ⅲ）与炔基配位后，降低炔基反键轨道π（C1—C2）*的能级，减小炔基反键轨道π（C1—C2）*与羰基氧原子孤对电子占据轨道2p （LP）C=O的能级差，促进羰基氧原子的孤对电子向反键轨道π（C1—C2）*转移，使羰基-炔基之间的亲核环化反应势垒下降.另外，当用氢原子替代反应底物炔基上连接的苯基时，速率控制步骤的反应势垒升高，反应活性下降.

Abstract：

By using the B3LYP method of density functional theory(DFT) with 6-311++G(d,p) basis set,the synthesis mechanism of unsaturated carbonyl-oxaspiro via AuCl3-catalyzed 2-hydroxy-2-(ethynyl)cyclohexanone was studied.The results suggest that the overall reaction of the most favorable channel includes five steps:activation of the ethynyl,nucleophilic cyclization reaction between carbonyl-oxygen and ethynyl-carbon,formation of the spiro-carbon,intermolecular hydrogen transfer,and regeneration of the catalyst.The catalysis key of AuCl3 is that its coordination with the ethynyl decreases the anti-bonding orbital energy of the π(C1—C2)*,and the orbital energy-gap between π(C1—C2)* and 2p-(LP)C=O,which promotes the electron transfer from LP-(2p)C=O orbital to π(C1—C2)* orbital,and decreases the forward reaction energy barrier of the nucleophilic cyclization between carbonyl-oxygen and ethynyl-carbon.Moreover,this study indicates that while the phenyl group connected the ethynyl is replaced by hydrogen atom,the forward reaction energy barrier of rate-controlling step increases and the overall reactivity decreases.

关键词

关键词： 密度泛函理论 ; 亲核环化反应 ; 双分子氢转移 ; 不饱和螺酮
Key words： density functional theory ; nucleophilic cyclization reaction ; intermolecular hydrogen transfer ; unsaturated carbonyl-oxaspiro

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