Biomimetic and Biocatalytic Synthesis of Bruceol. Issue 5 (28th December 2018)

• Record Type: Journal Article
• Authors: Day, Aaron J.; Lee, Joel H. Z.; Phan, Quang D.; Lam, Hiu C.; Ametovski, Adam; Sumby, Christopher J.; Bell, Stephen G.; George, Jonathan H.
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 5(2019)
• Page Start: 1427
• Page End: 1431
• Publication Date: 2018-12-28
• Subjects: biomimetic synthesis -- biosynthesis -- cascade reactions -- natural products -- total synthesis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201812432
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The first total synthesis of bruceol has been achieved using a biomimetic cascade cyclization initiated by a stereoselective Jacobsen–Katsuki epoxidation (and kinetic resolution) of racemic protobruceol‐I. A bacterial cytochrome P450 monooxygenase was also found to catalyze the conversion of protobruceol‐I into bruceol. The first full analysis of the NMR data of natural bruceol suggested that "isobruceol" was a previously unrecognized natural product also isolated from Philotheca brucei . This was confirmed by the re‐isolation, synthesis, and X‐ray analysis of isobruceol. In total, eight stereoisomers and structural isomers of bruceol have been synthesized in a highly divergent approach. Abstract : Bruceol almighty : Fifty‐five years after its isolation, the first total synthesis of bruceol has been achieved using a biomimetic cascade reaction. The original isolated sample of bruceol was used to help correct some historic structural misassignments.