Enantioselective Total Synthesis of (+)‐Jungermatrobrunin A. (3rd July 2019)

• Record Type: Journal Article
• Authors: Wu, Jinbao; Kadonaga, Yuichiro; Hong, Benke; Wang, Jin; Lei, Xiaoguang
• Is Part Of: Angewandte Chemie. Volume 131:Number 32(2019)
• Page Start: 10995
• Page End: 10999
• Publication Date: 2019-07-03
• Subjects: Peroxide -- Photochemie -- Radikalische Cyclisierungen -- Umlagerungen -- Totalsynthesen; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201903682
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A concise and enantioselective total synthesis of (+)‐jungermatrobrunin A (1 ), which features a unique bicyclo[3.2.1]octene ring skeleton with an unprecedented peroxide bridge, was accomplished in 13 steps by making use of a late‐stage visible‐light‐mediated Schenck ene reaction of (−)‐1α, 6α‐diacetoxyjungermannenone C (2 ). Along the way, a UV‐light‐induced bicyclo[3.2.1]octene ring rearrangement afforded (+)‐12‐hydroxy‐1α, 6α‐diacetoxy‐ ent ‐kaura‐9(11), 16‐dien‐15‐one (4 ). These divergent photo‐induced skeletal rearrangements support a possible biogenetic relationship between (+)‐1, (−)‐2, and (+)‐4 . Abstract : Die drei Naturstoffe, die im Bild gezeigt werden, wurden durch enantioselektive Synthese in 12 bis 13 Stufen hergestellt. Diese Synthesen wurden durch divergente photoinduzierte Gerüstumlagerungen eines intermediären Bicyclo[3.2.1]octen‐basierten Ringsystems ermöglicht.