A reaction mode of carbene-catalysed aryl aldehyde activation and induced phenol OH functionalization.
A reaction mode of carbene-catalysed aryl aldehyde activation and induced phenol OH functionalization.
复制标题
卡宾催化芳基醛活化和诱导苯酚OH官能化的反应模式
DOI：
10.1038/ncomms15598
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发表时间：
2017-05-25
影响因子：
16.6
通讯作者：
Chi YR
中科院分区：
文献类型：
--
作者：
Chen X;Wang H;Doitomi K;Ooi CY;Zheng P;Liu W;Guo H;Yang S;Song BA;Hirao H;Chi YR
不对称卡宾有机催化的研究主要集中在非芳香族骨架碳原子的活化上。在这里，我们报告了一种卡宾催化的反应模式，允许芳醛活化和远程氧原子官能化。将卡宾催化剂添加到2-羟基芳醛的醛部分，最终能够实现脱芳构化和远程OH活化。催化过程产生一种以氧原子为反应中心的卡宾衍生中间体。廉价的非手性尿素助催化剂与卡宾催化剂协同工作，使反应的对映选择性得到一致的提高。鉴于天然产物和合成功能分子中广泛存在的芳香族基团和杂原子，我们预计我们的反应模式将显著扩大卡宾催化在不对称化学合成中的能力。
The research in the field of asymmetric carbene organic catalysis has primarily focused on the activation of carbon atoms in non-aromatic scaffolds. Here we report a reaction mode of carbene catalysis that allows for aromatic aldehyde activation and remote oxygen atom functionalization. The addition of a carbene catalyst to the aldehyde moiety of 2-hydroxyl aryl aldehyde eventually enables dearomatization and remote OH activation. The catalytic process generates a type of carbene-derived intermediate with an oxygen atom as the reactive centre. Inexpensive achiral urea co-catalyst works cooperatively with the carbene catalyst, leading to consistent enhancement of the reaction enantioselectivity. Given the wide presence of aromatic moieties and heteroatoms in natural products and synthetic functional molecules, we expect our reaction mode to significantly expand the power of carbene catalysis in asymmetric chemical synthesis.