Neighboring Nitrogen Atom-Induced Reactions of Azidoacetyl Hydrazides, including Unexpected Nitrogen-Nitrogen Bond Cleavage of the Hydrazide
Neighboring Nitrogen Atom-Induced Reactions of Azidoacetyl Hydrazides, including Unexpected Nitrogen-Nitrogen Bond Cleavage of the Hydrazide
复制标题
DOI：
10.3390/org3040035
复制
发表时间：
2022-12
期刊：
影响因子：
--
通讯作者：
Hiroki Tanimoto;Ryo Adachi;Aoi Otsuki;T. Tomohiro
中科院分区：
文献类型：
--
作者：
Hiroki Tanimoto;Ryo Adachi;Aoi Otsuki;T. Tomohiro
我们研究了α-叠氮乙酰基的酰肼类化合物，它们通过叠氮基与酰肼部分的N-H之间的分子内氢键作用表现出特异的点击反应性。在与一般的烷基叠氮化物的竞争性点击反应中，无痕和非无痕Staudinger-Bertozzi连接通过氢键的加速效应选择性地发生叠氮化物位点。然而，从无痕反应获得的产物进一步转化为杂环化合物。此外，在合成具有萘二甲酰亚胺的叠氮基乙酰肼的尝试中，发生叠氮基乙酰肼的氮-氮键断裂，得到还原的胺产物。这些意想不到的结果可以帮助设计用于成功的酰肼化合物的Staudinger-Bertozzi连接的分子，并开发新的氮-氮键断裂方法。
We studied the hydrazide compounds of the α-azidoacetyl group, which showed specific click reactivity by the intramolecular hydrogen bonding between the azido group and the N-H of the hydrazide moiety. In the competitive click reactions with a general alkyl azide, both traceless and non-traceless Staudinger-Bertozzi ligation occurred azide-site-selectively by the acceleration effect of the hydrogen bonding. However, the product obtained from the traceless reaction was further transformed into heterocyclic compounds. In addition, in an attempt at a synthesis of naphthalimide-possessing azidoacetyl hydrazide, nitrogen-nitrogen bond cleavage of the azidoacetyl hydrazides occurred to give the reduced amine product. These unexpected results could help design molecules for the successful Staudinger-Bertozzi ligation of the hydrazide compounds and develop a new nitrogen-nitrogen bond cleavage method.