Ligand‐Controlled Regiodivergence for Catalytic Stereoselective Semireduction of Allenamides
Ligand‐Controlled Regiodivergence for Catalytic Stereoselective Semireduction of Allenamides
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配体——受控区域发散催化烯丙酰胺的立体选择性半还原
DOI：
10.1002/chem.202103402
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Cui, Xin
中科院分区：
文献类型：
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作者：
Hajiloo Shayegan, Mojtaba;Li, Zhong‐Yuan;Cui, Xin
配体控制的区域分歧已被开发用于丙二烯酰胺的催化半还原，具有优异的化学和立体控制。该系统还首次提供了丙二烯催化区域发散半还原的实例。半还原的发散是通过在操作简单且温和的条件下使用相同的钯预催化剂进行配体转换来实现的。单齿配体 XPhos 专门促进选择性 1,2-半还原以产生烯丙基酰胺，而双齿配体 BINAP 完全将区域选择性转变为 2,3-半还原，产生 (E)-烯酰胺衍生物。
Ligand‐controlled regiodivergence has been developed for catalytic semireduction of allenamides with excellent chemo‐ and stereocontrol. This system also provides an example of catalytic regiodivergent semireduction of allenes for the first time. The divergence of the semireduction is enabled by ligand switch with the same palladium pre‐catalyst under operationally simple and mild conditions. Monodentate ligand XPhos exclusively promotes selective 1,2‐semireduction to afford allylic amides, while bidentate ligand BINAP completely switched the regioselectivity to 2,3‐semireduction, producing (E)‐enamide derivatives.