| Autor: |
Wang YB; College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China., Liu W; College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China., Li T; College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China., Lu Y; College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China., Yu YT; College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China., Liu HT; College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China., Liu M; Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, College of Science, Southern University of Science and Technology Guangming Advanced Research Institute Southern University of Science and Technology (SUSTech), Shenzhen, Guangdong 518055, China., Li P; Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, College of Science, Southern University of Science and Technology Guangming Advanced Research Institute Southern University of Science and Technology (SUSTech), Shenzhen, Guangdong 518055, China., Qian PC; College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China., Tang H; College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China., Guan J; College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China., Ye LW; State Key Laboratory of Physical Chemistry of Solid Surfaces and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China., Li L; College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China.; State Key Laboratory of Physical Chemistry of Solid Surfaces and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China. |
| Abstrakt: |
Due to the inherent challenges posed by the linear coordination of gold(I) complexes, asymmetric gold-catalyzed processes remain challenging, particularly in the atroposelective synthesis of axially chiral skeletons. Except for extremely few examples of intramolecular annulations, the construction of axial chirality via asymmetric gold-catalyzed intermolecular alkyne transformation is still undeveloped. Herein, a gold/HNTf 2 -cocatalyzed asymmetric diazo-alkyne annulation is developed, allowing the atroposelective and divergent synthesis of chiral non- C 2 -symmetric biaryls and arylquinones in generally good to excellent yield (up to 93% yield) and enantioselectivity (up to 99% ee), with broad substrate scope. Notably, this work represents the first gold-catalyzed atroposelective construction in an intermolecular manner. More interestingly, this strategy is successfully extended to the first asymmetric construction of seven-membered-ring atropisomers bearing one carbon-centered chirality in excellent diastereoselectivity and high enantioselectivity (up to 93% ee and 50:1 dr). Remarkably, the utility of this methodology is further illustrated by the successful application of a representative axially chiral ligand in a series of enantioselective reactions. Importantly, the Brønsted acid as a proton-shuttle cocatalyst significantly promotes this asymmetric annulation. Additionally, the origin of enantioselectivity of this annulation and the role of HNTf 2 are disclosed by density functional calculations and control experiments. |
