Synthesis of Azepines via a [6 + 1] Annulation of Ynenitriles with Reformatsky Reagents

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• 作者：Mitsuhiro Yoshimatsu ; Miki Tanaka ; Yu Fujimura ; Yukiteru Ito ; Yusuke Goto ; Yuka Kobayashi ; Hiroaki Wasada ; Noriyuki Hatae ; Genzoh Tanabe ; Osamu Muraoka
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：October 2, 2015
• 年：2015
• 卷：80
• 期：19
• 页码：9480-9494
• 全文大小：593K
• ISSN：1520-6904

文摘

A protocol for the direct synthesis of azepines using a hafnium(III)-catalyzed [6 + 1] annulation of N-tethered ynenitriles with Reformatsky reagents is reported. A broad range of 3-amino-2,7-dihydro-1H-azepine-4-carboxylates 4aa鈥?b>4he were obtained in high yields and with excellent functional group tolerance. The copper-mediated reactions of isolable Blaise intermediates (enamino esters 3), uniquely underwent 5-endo cyclization to afford the 尾-2,5-dihydropyrrolyl 伪,尾-unsaturated esters 5aa鈥?b>5fc, which exhibit anticancer activity.