Catalytic Enantioselective γ‐Selective Additions of 2‐Allylazaarenes to Activated Ketones. Issue 13 (27th February 2017)

• Record Type: Journal Article
• Authors: Bai, Xiangbin; Zeng, Guangkuo; Shao, Tianju; Jiang, Zhiyong
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 13(2017)
• Page Start: 3684
• Page End: 3688
• Publication Date: 2017-02-27
• Subjects: allylic compounds -- arenes -- heterocycles -- organocatalysis -- synthetic methods; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201700190
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Reported herein is the first example of 2‐allylazaarenes in asymmetric catalysis. Highly γ‐selective allylation was demonstrated for activated ketones, including isatins and trifluoromethyl ketones. In the presence of either an amino‐acid‐based tertiary amine or quaternary ammonium salt catalyst, two series of tertiary hydroxy‐containing moieties were installed at the remote δ‐position of azaarenes in good chemical yields, excellent enantioselectivities, and E / Z ratios. The success of current γ‐selective reactions should provide inspiration for expansion to other allylazaarene derivatives and would open up new paradigms for the synthesis of chiral γ‐ and/or δ‐functionalized azaarenes. Abstract : Remote functionalization : The excellent γ‐selectivity of 2‐allylazaarenes was realized in allylation reactions with activated ketones, including isatins and trifluoromethyl ketones. In the presence of either an amino‐acid‐based tertiary amine or quaternary ammonium salt, two series of tertiary hydroxy‐containing moieties were successfully introduced at the remote δ‐position of azaarenes.