Synthesis of Aryl Amine Derivatives from Benzyl Nitriles via Electrocyclization of in Situ Generated N-Silyl Ketene Imines
Synthesis of Aryl Amine Derivatives from Benzyl Nitriles via Electrocyclization of in Situ Generated N-Silyl Ketene Imines
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通过原位生成的 N-甲硅烷基烯酮亚胺电环化从苄基腈合成芳胺衍生物
DOI：
10.1021/acs.orglett.6b00490
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发表时间：
2016
期刊：
影响因子：
5.2
通讯作者：
Keiji Tanino
中科院分区：
文献类型：
--
作者：
Fumihiko Yoshimura;Taiki Abe;Keiji Tanino
报道了N-硅基烯酮亚胺在有机合成中的反应活性。在两组温和的硅烷化条件下，邻位含烯基或芳基的苄腈均能顺利地以良好的产率转化为芳胺：（1）在非碱性条件下，使用TMSNTf 2-iPr 2NEt;（2）在碱性阴离子条件下，使用二异丙基酰胺-三异丙基氯硅烷锂（LDA-TIPSCl）。该反应可能是通过原位生成一个N-甲硅烷基乙烯酮亚胺，然后进行6π-电环化和芳构化。
The previously unexplored reactivity ofN-silyl ketene imines in organic synthesis is reported. Benzyl nitriles containing an alkenyl or aryl group at theorthoposition were smoothly converted into aryl amines in good yields under two sets of mild silylation conditions: (1) nonbasic conditions using TMSNTf2–iPr2NEt or (2) basic anionic conditions using lithium diisopropylamide–triisopropylsilyl chloride (LDA–TIPSCl). The reaction probably proceeds via in situ generation of anN-silyl ketene imine followed by 6π-electrocyclization and aromatization.