Chen Hua-Hong, Chen Yang-Bo, Gao Jun-Zhe, Ye Long-Wu, Zhou Bo
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, 361005, Xiamen, China.
State Key Laboratory of Organometallic Chemistry, Shanghai, Institute of Organic Chemistry, Chinese Academy of Sciences, 200032, Shanghai, China.
Angew Chem Int Ed Engl. 2024 Dec 16;63(51):e202411709. doi: 10.1002/anie.202411709. Epub 2024 Oct 30.
The dehydro-Diels-Alder (DDA) reaction is a powerful method for the construction of aromatic compounds. However, the enantioselective DDA reaction has been rarely developed, probably due to the competitive thermal reaction. Herein, we report a copper-catalyzed enantioselective DDA reaction through vinyl cation pathway. The reaction leads to the atom-economical synthesis of axially chiral phenyl and indolyl carbazoles in generally excellent yields with good to excellent atroposelectivities. This methodology represents the first example of non-noble metal-catalyzed enantioselective DDA reaction. Notably, new chiral ligand and organocatalyst derived from the constructed axially chiral carbazole are demonstrated to be useful in asymmetric catalysis.
脱氢狄尔斯-阿尔德（DDA）反应是构建芳香族化合物的一种有效方法。然而，对映选择性DDA反应很少被开发，这可能是由于存在竞争性的热反应。在此，我们报道了一种通过乙烯基阳离子途径的铜催化对映选择性DDA反应。该反应能以通常优异的产率和良好至优异的对映选择性实现轴向手性苯基和吲哚基咔唑的原子经济性合成。该方法代表了非贵金属催化对映选择性DDA反应的首例。值得注意的是，由构建的轴向手性咔唑衍生的新型手性配体和有机催化剂被证明可用于不对称催化。
