Asymmetric Synthesis of Chiral Calix[4]arenes with Both Inherent and Axial Chirality via Cobalt-Catalyzed Enantioselective Intermolecular C-H Annulation.

Autor: Qian PF; Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China., Zhou G; Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China., Hu JH; Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China., Wang BJ; Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China., Jiang AL; Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China., Zhou T; Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China., Yuan WK; Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China., Yao QJ; Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China., Chen JH; Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China., Kong KX; Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China., Shi BF; Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China.; College of Material Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou, 311121, China.; School of Chemistry and Chemical Engineering, Henan Normal University, Henan, 453007, China.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Dec 20; Vol. 63 (52), pp. e202412459. Date of Electronic Publication: 2024 Nov 02.
DOI: 10.1002/anie.202412459
Abstrakt: Inherently chiral calixarenes have garnered significant attention due to their distinctive properties, yet the development of efficient catalytic asymmetric synthesis methods remains a critical challenge. Herein, we report the asymmetric synthesis of calix[4]arenes featuring inherent or both inherent and axial chirality via a cobalt-catalyzed C-H activation/annulation strategy in high yield with excellent enantio- and diastereoselectivity (up to >99 % ee and >20 : 1 dr). Electrooxidation was also suitable for this transformation to obviate the sacrificial metal oxidants, underscoring the environmentally friendly potential of this approach. A key octahedral cobaltacycle intermediate was synthesized and characterized, providing valuable insights into the mode of enantio- and diastereocontrol of this protocol. Noteworthy photoluminescence quantum yields of up to 0.94 were measured, underscoring the potential of these compounds in the domain of organic fluorescent materials.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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