Takami S, Oshida A, Tawada Y, Kashino S, Satake K, Kimura M
Institute for Fundamental Research of Organic Chemistry (IFOC), Kyushu University, Hakozaki 6-10-1, Higashi-ku, Fukuoka 812-8581, Japan, and Department of Chemistry, Faculty of Science, Okayama University, Tsushima-Naka 3-1-1, Okayama 700-8.
J Org Chem. 2000 Sep 22;65(19):6093-6. doi: 10.1021/jo000540e.
Oxidation reactions of 2,5- and 3,6-di-tert-butyl-3H-azepines (1 and 2) with selenium dioxide (SeO(2)) were performed. The oxidation of 1 with SeO(2) gave 3-tert-butyl-7,7-dimethyl-4-oxo-octa-2,5-dienal 3 in 36% yield, 4-tert-butyl-5-(3,3-dimethyl-2-oxo-butylidene)-1, 5-dihydro-pyrrol-2-one 4 in 13% yield, 2, 6-di-tert-butyl-2-pyridinecarbaldehyde 5 in 12% yield, and 4, 7-di-tert-butyl-2H-azepin-2-one (2-azatropone) 6 in 6% yield, respectively. Oxidation of 2 with SeO(2) gave 2, 2-dimethyl-1-[2-(5-tert-butyl)-pyridyl]propanol 7 in 55% yield, and 3,6-di-tert-butyl-2H-azepine 8 in 5% yield, respectively. We found that selenium dioxide oxidation of 1 affords 4-oxo-octa-2,5-dienal 3 by a new ring cleavage reaction of 1, and we described the first synthesis of 2-azatropone 6 from this oxidation of 1. In the case of 2, pyridylpropanol 7 was obtained as the major product. We now report in detail result of these oxidation reactions, which have led to the synthesis of a novel azatropone derivative.
进行了2,5 - 二 - 叔丁基 - 3H - 氮杂䓬（1）和3,6 - 二 - 叔丁基 - 3H - 氮杂䓬（2）与二氧化硒（SeO₂）的氧化反应。1与SeO₂的氧化反应分别以36%的产率得到3 - 叔丁基 - 7,7 - 二甲基 - 4 - 氧代 - 辛 - 2,5 - 二烯醛3、13%的产率得到4 - 叔丁基 - 5 -（3,3 - 二甲基 - 2 - 氧代 - 亚丁基）- 1,5 - 二氢 - 吡咯 - 2 - 酮4、12%的产率得到2,6 - 二 - 叔丁基 - 2 - 吡啶甲醛5以及6%的产率得到4,7 - 二 - 叔丁基 - 2H - 氮杂䓬 - 2 - 酮（2 - 氮杂环庚三烯酮）6。2与SeO₂的氧化反应分别以55%的产率得到2,2 - 二甲基 - 1 - [2 -（5 - 叔丁基）- 吡啶基]丙醇7以及5%的产率得到3,6 - 二 - 叔丁基 - 2H - 氮杂䓬8。我们发现1与二氧化硒的氧化反应通过1的一种新的开环反应得到4 - 氧代 - 辛 - 2,5 - 二烯醛3，并且我们描述了从1的这种氧化反应首次合成2 - 氮杂环庚三烯酮6。在2的情况下，吡啶基丙醇7是主要产物。我们现在详细报道这些氧化反应的结果，这些结果已导致一种新型氮杂环庚三烯酮衍生物的合成。
