Enantioselective Total Syntheses of Preussomerins: Control of Spiroacetal Stereogenicity by Photochemical Reaction of a Naphthoquinone through 1, 6‐Hydrogen Atom Transfer. (21st December 2022)

• Record Type: Journal Article
• Authors: Ando, Yoshio; Ogawa, Daichi; Ohmori, Ken; Suzuki, Keisuke
• Is Part Of: Angewandte Chemie. Volume 135:Number 5(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-12-21
• Subjects: Photochemical Reactions -- Preussomerins -- Redox Chemistry -- Stereospecificity -- Total Synthesis; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202213682
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: We report the enantioselective total syntheses of preussomerins EG1, EG2, and EG3 . The key transformation is a stereospecific photochemical reaction involving 1, 6‐hydrogen atom transfer to achieve retentive replacement of a C−H with a C−O bond, enabling otherwise‐difficult control of the spiroacetal stereogenic center. Abstract : Photochemical reactions of naphthoquinones triggered by 1, 6‐hydrogen atom transfer have been developed. This reaction proceeds in stereospecific manner without loss of the stereochemical information of the substrate, enabling the enantioselective total synthesis of preussomerin EGs. The constructed spiroacetal center is the sole stereogenic center in the product, which had been previously impossible to set by exploiting conventional methods.