Rh2(II)-catalyzed intramolecular aliphatic C-H bond amination reactions using aryl azides as the N-atom source.

Rh2(II)-catalyzed intramolecular aliphatic C-H bond amination reactions using aryl azides as the N-atom source.
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DOI:
10.1021/ja301519q
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发表时间:
2012-05-02
影响因子:
15
通讯作者:
Driver, Tom G.
Driver, Tom G.
中科院分区:
化学1区
文献类型:
--
作者:
Quyen Nguyen;Sun, Ke;Driver, Tom G.

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人们发现二羧酸铑 (II) 络合物可以使用芳基叠氮化物作为 N 原子前体催化未活化的伯、仲或叔脂肪族 C-H 键的分子内胺化。虽然氮原子上通常需要强吸电子基团来实现该反应,但我们发现富电子和缺电子芳基叠氮化物都是金属氮烯反应中间体的有效来源。
Rhodium(II) dicarboxylate complexes were discovered to catalyze the intramolecular amination of unactivated primary-, secondary-, or tertiary aliphatic C–H bonds using aryl azides as the N-atom precursor. While a strong electron-withdrawing group on the nitrogen atom is typically required to achieve this reaction, we found that both electron-rich- and electron-poor aryl azides are efficient sources for the metal nitrene reactive intermediate.
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