Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
Institute of Pharmaceutical Science and Technology, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China.
Org Lett. 2023 Jun 30;25(25):4740-4744. doi: 10.1021/acs.orglett.3c01746. Epub 2023 Jun 21.
Reported herein is the catalytic asymmetric aminative dearomatization reaction of common phenols. As opposed to the well-studied indoles and naphthols, phenols are supposed to be challenging substrates for catalytic asymmetric dearomatization reactions in terms of their strong aromaticity and regioselectivity issues. Under the catalysis of a chiral phosphoric acid, the C4-regiospecific aminative dearomatization of phenols with azodicarboxylates readily occurred at ambient temperature, delivering an array of biologically and synthetically important aza-quaternary carbon cyclohexadieneones in good yields and with excellent enantioselectivities (29 examples, up to 98% yield, and >99% ee).
本文报道了常见酚类化合物的催化不对称氨基去芳构化反应。与研究充分的吲哚和萘酚不同，酚类化合物由于其强芳香性和区域选择性问题，被认为是催化不对称去芳构化反应具有挑战性的底物。在手性磷酸的催化下，室温下，偶氮二甲酸酯与酚类化合物的 C4-区域选择性氨基去芳构化反应很容易发生，以良好的收率和优异的对映选择性（29 个实例，最高达 98%的产率和>99%的对映体过量值）得到一系列具有生物和合成重要性的氮杂季碳环己二烯酮。
