ORTHO METALATION DIRECTED BY ALPHA-AMINO ALKOXIDES
ORTHO METALATION DIRECTED BY ALPHA-AMINO ALKOXIDES
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DOI：
10.1021/jo00180a024
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发表时间：
1984-01-01
影响因子：
3.6
通讯作者：
BROWN, JD
中科院分区：
文献类型：
--
作者：
COMINS, DL;BROWN, JD
将芳香醛与苯或四氢呋喃中的某些二烷基酰胺锂加成，得到正氨基醇盐，该醇盐被过量的正丁基锂邻位锂化。随后的烷基化和水解通过一锅反应提供邻位取代的芳香醛。研究了衍生自 1-和 2-萘醛以及各种取代苯甲醛的氨基醇盐的邻位金属化。当使用，，-甲基乙二胺作为α-氨基醇盐的胺组分时，金属化可以在较低的温度下进行。这种速率的增加是由于分子内 TMEDA 辅助金属化。讨论了这种邻位金属化的合成用途，包括改变氨基醇盐的胺成分如何影响区域化学和金属化速率。
The addition of aromatic aldehydes to certain lithium dialkylamides in benzene or tetrahydrofuran gave «-amino alkoxides which were ortho lithiated with excess n-butyllithium. Subsequent alkylation and hydrolysis provided ortho-substituted aromatic aldehydes via a one-pot reaction. The ortho metalation of-amino alkoxides derived from 1-and 2-naphthaldehyde and various substituted benzaldehydes was examined. When,,'--methylethylenediamine was used as the amine component of the-amino alkoxide, metalation could be carried out at lower temperatures. This rate increase is due to an intramolecular TMEDA-like assisted metalation. The synthetic utility of this ortho metalation, including how varying the amine component of the-amino alkoxide affects the regiochemistry and metalation rate, is discussed.