Mechanism of the Gold-Catalyzed Rearrangement of (3-Acyloxyprop-1-ynyl)oxiranes: A Dual Role of the Catalyst
Mechanism of the Gold-Catalyzed Rearrangement of (3-Acyloxyprop-1-ynyl)oxiranes: A Dual Role of the Catalyst
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DOI：
10.1021/jo802516k
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发表时间：
2009-04-17
影响因子：
3.6
通讯作者：
de Lera, Angel R.
中科院分区：
文献类型：
--
作者：
Gonzalez Perez, Adan;Silva Lopez, Carlos;de Lera, Angel R.
[图表] 1重排的三种竞争路径（涉及1，2-和1，3-酯迁移与炔或环氧乙烷活化）证明了金作为催化剂的多方面特征。这种有用的合成转化的最有利机制涉及八个以上步骤的级联。在基板中的所有功能基团发挥关键和协同作用，和顺序的金协调的π-系统和孤对氧是必要的。这三种途径的探索表明使用非亲炔刘易斯酸（BF 3）作为这种转化的可能的合成替代品。
[GRAPHICS]The three competing paths for the rearrangement of 1 (involving 1,2- and 1,3-ester migration with alkyne or oxirane activation) evidence the multifaceted character of gold as a catalyst. The most favorable mechanism for this useful synthetic transformation involves a cascade of more than eight steps. All the functional groups in the substrate play a crucial and synergistic role, and sequential gold coordination to both the pi-system and the lone pairs of oxygen is needed. Exploration of these three paths suggests the use of a nonalkynophilic Lewis acid (BF3) as a possible synthetic alternative for this transformation.