The nature and role of 8-deltacyclyl and 7-isodeltacyclyl cations in solvolytic reactions of parent brosylates
The nature and role of 8-deltacyclyl and 7-isodeltacyclyl cations in solvolytic reactions of parent brosylates
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DOI：
10.1021/jo010897y
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发表时间：
2002-05-31
影响因子：
3.6
通讯作者：
Dacres, JE
中科院分区：
文献类型：
--
作者：
Freeman, PK;Dacres, JE
外消旋-8-三环基溴磺酸酯的溶剂分解直接通过C-2离域阳离子进行，得到外消旋-8-三环基乙酸酯。的内差向异构体的溶剂分解提出了一个更复杂的图片，反应通过一个经典的deltacyclyl阳离子，非经典的C-2离域阳离子，和isodeltacyclyl阳离子。外消旋-7-异三环基溴磺酸酯的溶剂分解产生7-异三环基离子，随后产生C2离域的三环基阳离子，形成8-三环基乙酸酯和外消旋-7-异三环基乙酸酯。采用密度泛函方法在B3LYP/6 - 311 + G（3df，2p）//B3LYP/6 - 31G（d）和BPW91/6 - 311 + G（3df，2p）//BPW91/6 - 31G（d）水平上对这三个相关反应流形中的阳离子中间体进行了表征.
Solvolysis of exo-8-deltacyclyl brosylate proceeds directly through a C-2 delocalized cation to exo-8-deltacyclyl acetate. The solvolysis of the endo epimer presents a more complex picture, reacting via a classical deltacyclyl cation, the nonclassical C-2 delocalized cation, and the isodeltacyclyl cation. The solvolysis of exo-7-isodeltacyclyl brosylate generates the 7-isodeltacyclyl ion and subsequently the C2 delocalized deltacyclyl cation forming 8-deltacyclyl acetate and exo-7-isodeltacyclyl acetate. The cationic intermediates in these three related reaction manifolds are characterized using density functional methods at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d) and BPW91/6-311+G(3df, 2p)//BPW91/6-31G(d) levels.