Radical Photocyclization Route for Macrocyclic Lactone Ring Expansion and Conversion to Macrocyclic Lactams and Ketones

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• 作者：Keisuke Nishikawa ; Yasuharu Yoshimi ; Kousuke Maeda ; Toshio Morita ; Ichiro Takahashi ; Tatsuya Itou ; Sho Inagaki ; Minoru Hatanaka
• 刊名：The Journal of Organic Chemistry
• 出版年：2013
• 出版时间：January 18, 2013
• 年：2013
• 卷：78
• 期：2
• 页码：582-589
• 全文大小：359K
• 年卷期：v.78,no.2(January 18, 2013)
• ISSN：1520-6904

文摘

A new method for the synthesis of macrocyclic lactones, lactams, and ketones, which utilizes photoinduced intramolecular radical cyclization reactions of substrates containing tethered carboxylic acids and 伪,尾-unsaturated carbonyl moieties, has been uncovered. Photocyclization of the carboxylic acids tethered acrylate ester, which were prepared starting from the macrocyclic lactones, gave the two-carbon elongated macrocyclic lactones via decarboxylation. Similar photoreactions of carboxylic acid tethered acryl amide or 伪,尾-unsaturated ketone moieties, which were also prepared starting from the macrocyclic lactones, produced macrocyclic lactams or ketones, respectively. The simple approach can be readily applied to the preparation of a variety of macrocyclic lactones, lactams, and ketones with tunable ring sizes.