Transformation of the sp2 Carbanion to Carbene with Subsequent 1,1-Migratory Insertion and Nucleophilic Substitution in Rare-Earth Metal Chemistry.
Transformation of the sp2 Carbanion to Carbene with Subsequent 1,1-Migratory Insertion and Nucleophilic Substitution in Rare-Earth Metal Chemistry.
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DOI：
10.1021/acs.inorgchem.1c02589
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发表时间：
2021-11
影响因子：
4.6
通讯作者：
Zeming Huang;Ruru Wang;Tian Sheng;Xiangyang Zhong;Shaowu Wang;Xiancui Zhu;Qingbing Yuan;Yun Wei-Yun-W
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文献类型：
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作者：
Zeming Huang;Ruru Wang;Tian Sheng;Xiangyang Zhong;Shaowu Wang;Xiancui Zhu;Qingbing Yuan;Yun Wei-Yun-W
使用早期过渡金属开发费歇尔型亲电卡宾化学一直是一个巨大的挑战，因为此类金属在高氧化态时缺乏 d 电子来稳定亲电卡宾。在此，我们首次公开了通过电子转移将处于高氧化态的稀土金属与 d0 电子一起将 sp2 碳负离子原位转化为 Fischer 型亲电子卡宾的实验和理论发现。卡宾可以进行1,1-迁移插入到相邻的RE-C(sp3)键中，当卡宾用特殊的有机锂试剂o-Me2NC6H4CH2Li进行亲核取代时，配体的吲哚环会发生前所未有的开环。成功的关键是独特定制的新型配体系统，该系统具有合适的共轭结构单元（-C=C-C=N），带有与稀土金属中心连接的sp2碳负离子。
The development of Fischer-type electrophilic carbene chemistry with early transition metals has been a great challenge due to the fact that such metals in their high oxidation states lack the d electrons to stabilize the electrophilic carbene. Herein, we disclose the first experimental and theoretical findings of in situ transformation of an sp2 carbanion to a Fischer-type electrophilic carbene with rare-earth metals in their high oxidation state with a d0 electron via electron transfer. The carbene may undergo 1,1-migratory insertion into an adjacent RE-C(sp3) bond, and an unprecedented ring opening of the indole ring of the ligand occurs when the carbenes undergo nucleophilic substitution with a special organolithium reagent o-Me2NC6H4CH2Li. The key to success is the uniquely tailored novel ligand systems featuring a suitable conjugate building block (-C═C-C═N) bearing an sp2 carbanion connected to the rare-earth metal center.