Hydrogen Bonding Networks Enable Brønsted Acid‐Catalyzed Carbonyl‐Olefin Metathesis. Issue 13 (10th February 2022)

• Record Type: Journal Article
• Authors: Anh To, Tuong; Pei, Chao; Koenigs, Rene M.; Vinh Nguyen, Thanh
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 13(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-02-10
• Subjects: Brønsted Acid Catalysis -- Carbonyl-Olefin Metathesis -- HFIP -- Hydrogen-Bonding -- Perfluorinated Solvent; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202117366
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Synthetic chemists have learned to mimic nature in using hydrogen bonds and other weak interactions to dictate the spatial arrangement of reaction substrates and to stabilize transition states to enable highly efficient and selective reactions. The activation of a catalyst molecule itself by hydrogen‐bonding networks, in order to enhance its catalytic activity to achieve a desired reaction outcome, is less explored in organic synthesis, despite being a commonly found phenomenon in nature. Herein, we show our investigation into this underexplored area by studying the promotion of carbonyl‐olefin metathesis reactions by hydrogen‐bonding‐assisted Brønsted acid catalysis, using hexafluoroisopropanol (HFIP) solvent in combination with para ‐toluenesulfonic acid (pTSA). Our experimental and computational mechanistic studies reveal not only an interesting role of HFIP solvent in assisting pTSA Brønsted acid catalyst, but also insightful knowledge about the current limitations of the carbonyl‐olefin metathesis reaction. Abstract : H‐bonding network: Hexafluoroisopropanol (HFIP) can act as a hydrogen‐bond donor to enhance the catalytic efficiency of simple Brønsted acid catalysts in carbonyl‐olefin metathesis reactions by stabilization of all transition states and intermediates along the reaction pathway.