Anion translocation in organolithiums: A mechanism for the lithiation and cyclisation of tertiary naphthamides
Anion translocation in organolithiums: A mechanism for the lithiation and cyclisation of tertiary naphthamides
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DOI：
10.1016/s0040-4039(98)01291-x
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发表时间：
1998-08-20
影响因子：
1.8
通讯作者：
Rowley, M
中科院分区：
文献类型：
--
作者：
Ahmed, A;Clayden, J;Rowley, M
氚标记表明，分子内质子转移(“阴离子转移”)是导致α-锂基叔萘胺并由此产生阴离子环化产物的机制的关键步骤。动力学同位素效应意味着质子从邻位转移可以成为α-锂化合的唯一机制，尽管对于未氚的酰胺也有一个平行的机制，其中锂化直接发生在α到氮的位置上。(C)1998爱思唯尔科学有限公司。保留所有权利。
Deuterium labelling shows that an intramolecular proton transfer ("anion translocation") is a key step in the mechanism leading to an alpha-lithiated tertiary naphthamide and thence to the products of anionic cyclisation. The kinetic isotope effect means that proton transfer from the ortho position can become the sole mechanism for alpha-lithiation, though for undeuterated amides a parallel mechanism also operates in which lithiation occurs directly at the position alpha to nitrogen. (C) 1998 Elsevier Science Ltd. All rights reserved.