Rhodium-CatalyzedN-tert-Butoxycarbonyl (Boc) Amination by Directed CH Bond Activation
Rhodium-CatalyzedN-tert-Butoxycarbonyl (Boc) Amination by Directed CH Bond Activation
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DOI：
10.1002/adsc.201600410
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发表时间：
2016-06
影响因子：
5.4
通讯作者：
Julian Wippich;Nadina Truchan;T. Bach
中科院分区：
文献类型：
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作者：
Julian Wippich;Nadina Truchan;T. Bach
n -叔丁基羰基叠氮化物（BocN3）被证明是一种有效和经济的将N-Boc保护的氨基直接引入噻吩和苯核的来源。2-吡啶-2-基噻吩胺化反应（10例）得率为52 ~ 88%。对于各苯的胺化反应（10个例子），记录了54%至99%之间的产率，并且对带有吸电子基团的底物观察到改善的反应性。将该反应应用于吲哚喹啉类生物碱喹多啉和隐托平的短时间全合成。轻松去除Boc保护基团是合成成功的关键。将反应范围扩展到C(sp3)H键胺化和2-苯氧恶唑啉胺化。对于2-吡啶-2-基苯的胺化反应，动力学氘同位素效应为2.0。
N-tert-Butoxycarbonyl azide (BocN3) was shown to be an efficient and economic source for the directed introduction of N-Boc protected amino groups into the thiophene and benzene nucleus. Yields for the amination of 2-pyridin-2-ylthiophenes (10 examples) were 52–88%. For the amination of the respective benzenes (10 examples) yields between 54% and 99% were recorded with an improved reactivity observed for substrates that bear an electron-withdrawing group. The reaction was applied to short total syntheses of the indoloquinoline alkaloids quindoline and cryptolepine. The facile removal of the Boc protecting group was the key to the success of the syntheses. The scope of the reaction was extended to a C(sp3)H bond amination and to the amination of 2-phenyloxazoline. For the amination of 2-pyridin-2-ylbenzene a kinetic deuterium isotope effect of 2.0 was determined.