Catalytic Reductive Cross Coupling and Enantioselective Protonation of Olefins to Construct Remote Stereocenters for Azaarenes
- 2 March 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 143 (10), 4024-4031
- https://doi.org/10.1021/jacs.1c01073
Abstract
A novel enantioselective protonation protocol that is triggered by reductive cross coupling of olefins is reported. When under cooperative photoredox and chiral hydrogen-bonding catalytic conditions and using a terminal reductant, various alpha-branched vinylketones with diverse vinylazaarenes could provide important enantioenriched azaarene derivatives containing tertiary stereocenters at their remote delta-position with high yields and enantioselectivities. This reaction system is also suitable for alpha-branched vinylazaarenes, thus successfully assembling elusive 1,4-stereocenters. The convenient late-stage modifications of products, especially the formation of remote epsilon-tertiary and epsilon-heteroquaternary carbon stereocenters, further highlight the important synthetic value of this method. Control experiments and density functional theory (DFT) calculations were conducted to elucidate the plausible reaction mechanism and origins of regioselectivity and stereoselectivity.Keywords
Funding Information
- Henan Normal University
- National Natural Science Foundation of China (21901062, 21925103)
- Henan University
- Key Technologies R&D Program of Henan (202102310005)
This publication has 57 references indexed in Scilit:
- Photochemical Strategies for Carbon–Heteroatom Bond FormationEuropean Journal of Organic Chemistry, 2019
- Beyond Friedel and Crafts: Innate Alkylation of C−H Bonds in ArenesAngewandte Chemie, 2019
- Photochemical C–H bond coupling for (hetero)aryl C(sp2)–C(sp3) bond constructionOrganic & Biomolecular Chemistry, 2019
- Recent Advances in Minisci‐Type ReactionsAngewandte Chemie, 2019
- Advancements in Visible-Light-Enabled Radical C(sp)2–H Alkylation of (Hetero)arenesSynthesis, 2019
- Construction and Functionalization of Heteroarenes by Use of Photoredox CatalysisEuropean Journal of Organic Chemistry, 2017
- Visible Light Photocatalysis for the Generation and Use of Reactive Azolyl and Polyfluoroaryl IntermediatesAccounts of Chemical Research, 2016
- C═N-Containing Azaarenes as Activating Groups in Enantioselective CatalysisThe Journal of Organic Chemistry, 2013
- Chiral Brønsted acid catalyzed Friedel–Crafts alkylation reactionsChemical Society Reviews, 2009
- Catalytic Asymmetric Friedel−Crafts Alkylation Reactions—Copper Showed the WayChemical Reviews, 2008