Division of Chemistry &Biological Chemistry, School of Physical &Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Huaxi District, Guiyang 550025, China.
Nat Commun. 2017 May 25;8:15598. doi: 10.1038/ncomms15598.
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.
不对称卡宾有机催化领域的研究主要集中在激活非芳环骨架中的碳原子。在这里，我们报告了一种卡宾催化的反应模式，它允许芳基醛的激活和远程氧原子功能化。将卡宾催化剂添加到 2-羟基芳醛的醛部分最终可以实现去芳构化和远程 OH 激活。催化过程生成一种以氧原子为反应中心的卡宾衍生中间体。廉价的手性脲共催化剂与卡宾催化剂协同作用，一致提高反应的对映选择性。鉴于芳香族部分和杂原子在天然产物和合成功能分子中的广泛存在，我们预计我们的反应模式将显著扩展卡宾催化在不对称化学合成中的应用。
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