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Novel Organocatalytic Activation of Unmodified Morita–Baylis–Hillman Alcohols for the Synthesis of Bicyclic α‐Alkylidene‐Ketones |
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| Authors: | Dr. Julian Stiller Dorota Kowalczyk Dr. Hao Jiang Prof. Dr. Karl Anker Jørgensen Dr. Łukasz Albrecht |
| Affiliation: | 1. Center for Catalysis, Chemistry Department, Aarhus University, Langelandsgade 140, 8000 Aarhus C (Denmark);2. Institute of Organic Chemistry, Chemistry Department, Lodz University of Technology, ?eromskiego 116, 90‐924 ?ód? (Poland) |
| Abstract: | The organocatalytic activation of Morita–Baylis–Hillman alcohols via H‐bonding‐iminium‐ion formation is demonstrated for the first time. This activation strategy enables the Morita‐Baylis–Hillman alcohols to undergo a formal SN2′ reaction. In combination with the well‐established enamine reactivity, this creates a new reactivity pattern. The application of this new activation mode for the synthesis of bicyclic α‐alkylidene‐ketones is demonstrated. The developed reaction sequence proceeds efficiently affording nature‐inspired target products with four contiguous stereogenic centers in a highly stereoselective manner. |
| Keywords: | activation strategies alpha‐alkylidene‐ketones asymmetric synthesis Morita– Baylis– Hillman adducts organocatalysis |