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氮杂降蒈基氨自由基的区域选择性重排为 2,8-二氮杂双环[3.2.1]辛-2-烯体系的研究。

Studies on the Regioselective Rearrangement of Azanorbornanic Aminyl Radicals into 2,8-Diazabicyclo[3.2.1]oct-2-ene Systems.

机构信息

Departamento de Química Orgánica (Facultad de Química), Universidad de Sevilla, C/ Prof. García González, 1, 41012Sevilla, Spain.

Center for Cooperative Research in Biosciences (CIC bioGUNE), Basque Research and Technology Alliance (BRTA), Bizkaia Technology Park, Building 800, 48160Derio, Spain.

出版信息

J Org Chem. 2022 Dec 16;87(24):16483-16491. doi: 10.1021/acs.joc.2c02201. Epub 2022 Dec 1.

DOI:10.1021/acs.joc.2c02201
PMID:36455216
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9764359/
Abstract

Aminyl radicals are nitrogen-centered radicals of interest in synthetic strategies involving C-N bond formation due to their high reactivity. These intermediate radicals are generated by the reaction of an organic azide with tributyltin hydride (BuSnH) in the presence of substoichiometric amounts of azobisisobutyronitrile (AIBN). In this work, we report the regioselective rearrangement of azanorbornanic ([2.2.1]azabicyclic) aminyl radicals into 2,8-diazabicyclo[3.2.1]oct-2-ene systems. With the aim to establish the structural requirements for this ring expansion, we have studied the effect of different bridgehead atoms of the [2.2.1]bicyclic system and the presence of an alkyl substituent at C4. Attempts to perform this ring expansion on a monocyclic analogue have been also explored to evaluate the influence of the bicyclic skeleton on the rearrangement. A detailed mechanistic proposal supported by computational studies is reported.

摘要

氨基金属自由基是氮中心自由基，由于其高反应性，在涉及 C-N 键形成的合成策略中引起了关注。这些中间自由基是通过有机叠氮化物与三丁基锡氢化物（BuSnH）在亚化学计量的偶氮二异丁腈（AIBN）存在下反应生成的。在这项工作中，我们报告了阿扎诺尔博纳米基（[2.2.1]氮杂双环）氨基金属自由基的区域选择性重排为 2,8-二氮杂双环[3.2.1]辛-2-烯体系。为了确定这种环扩张的结构要求，我们研究了[2.2.1]双环系统的不同桥头原子和 C4 上的烷基取代基的存在对环扩张的影响。还探索了在单环类似物上进行这种环扩张的尝试，以评估双环骨架对重排的影响。报告了由计算研究支持的详细的机理建议。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/71db874b019e/jo2c02201_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/0d92a50bbe74/jo2c02201_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/7542f3a0b897/jo2c02201_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/8915f9a3b4a9/jo2c02201_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/6cb40c53b8f9/jo2c02201_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/72019971a75d/jo2c02201_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/5aa086a01146/jo2c02201_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/71db874b019e/jo2c02201_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/0d92a50bbe74/jo2c02201_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/7542f3a0b897/jo2c02201_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/8915f9a3b4a9/jo2c02201_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/6cb40c53b8f9/jo2c02201_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/72019971a75d/jo2c02201_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/5aa086a01146/jo2c02201_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4b5/9764359/71db874b019e/jo2c02201_0002.jpg

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本文引用的文献

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