Catalytic Asymmetric Visible-Light de Mayo Reaction by ZrCl₄-Chiral Phosphoric Acid Complex

Abstract

Catalytic asymmetric de Mayo reaction was achieved for the first time under visible light using asymmetric binary acid catalysis (ABC) involving zirconium chloride and chiral phosphoric acid (CPA). The chiral zirconium catalysis enables effective reactions over a broad range of 1,3-diketones and alkenes with up to >99% yield and 98% ee. The key chiral zirconium enolate was isolated and characterized to account for the observed catalysis and stereoselectivity.

Enantioselective Synthesis of Homochiral Hierarchical Nd8Fe3-Oxo Cluster from Racemic Nd9Fe2-Oxo Cluster

“…A variety of materials are widely used in catalytic reactions, but due to the unknown precise structure of such materials, it is difficult to understand their structure–activity relationship from the atomic and molecular levels. − Chiral metal nanoclusters modified with abundant metal sites are expected to accomplish the straightforward enantioselective de Mayo reaction. − The catalytic performance of chiral cluster on the asymmetric de Mayo reaction between 1,3-diketones and alkenes is examined in Table . The de Mayo reaction between dibenzoylmethane and p -fluorostyrene gives rise to 1,5-pentanedione, 2-(4-fluorophenyl)-1,5-diphenyl, which was isolated and determined by 1 H NMR (Figure S29).…”

Photoinduced Generation of Active Intermediates from Unmodified 1,3‐Dicarbonyl Compounds for Organic Transformations

“…In the subsequent year, the same group conducted further investigations into this reaction and discovered that the introduction of chiral phosphoric acid complexes can accomplish the synthesis of chiral compounds via enantioselective de Mayo reaction (Scheme 39). [51] The highest yield exceeded 99 %, and the highest enantiomeric excess reached up to 98 %. Optimization of the reaction conditions revealed that using 5 mol % to 15 mol % of chiral phosphoric acid ligands and CHCl 3 as the solvent and irradiating with a 10 W 400 nm LED could maximize the enantiomeric excess of the target product.…”

Harnessing the Power of the De Mayo Reaction: Unveiling a Photochemical and Photocatalytic Masked [2+2] Methodology for Organic Synthesis

“…Very recently this year, Luo and co-workers developed the first visible light-mediated enantioselective de Mayo reaction through the photoexcitation of a chiral Zr-chiral phosphoric acid enolate complex (Scheme 28). [57] The enantioselectivity of the process is determined in the [2 + 2] photocycloaddition between the chiral Zr enolate and the olefin which is proposed to proceed following a triplet pathway. The reaction takes place with aryl-alkyl substituted 1,3-diketones with different styrenes and cyclic or linear aliphatic alkenes.…”