MECHANISM OF THE CLAISEN REARRANGEMENT OF ALLYL VINYL ETHERS
MECHANISM OF THE CLAISEN REARRANGEMENT OF ALLYL VINYL ETHERS
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DOI：
10.1021/ja00184a018
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发表时间：
1989-01-18
影响因子：
15
通讯作者：
JIE, CX
中科院分区：
文献类型：
--
作者：
DEWAR, MJS;JIE, CX
报道了烯丙基乙烯基醚及其23个衍生物的Claisen重排反应的AMI计算结果。预测的反应，正确地，发生优先通过椅子型过渡态，并优先导致E异构体。虽然一些反应被预测发生的两个替代路径，对应于替代同步和非同步机制，涉及过渡态，分别是芳香族和biradicaloid，这里的区别只是边缘，和大多数的反应tookplace由一个单一的独特的中间体类型的路径。
AMI calculations are reported for the Claisen rearrangements of allyl vinyl ether and 23 derivatives. The reactions are predicted, correctly, to take place preferentially via chair-type transition states and to lead preferentially to E isomers. While some of the reactions are predicted to take place by two alternative paths, corresponding to alternative synchronous and nonsynchronous mechanisms, involving transition states that are, respectively, aromatic and biradicaloid, the distinction here is only marginal, and most of the reactions tookplace by a single unique path of intermediate type.