Application of a Palladium‐Catalyzed C−H Functionalization/Indolization Method to Syntheses of cis‐Trikentrin A and Herbindole B. Issue 39 (29th August 2016)

• Record Type: Journal Article
• Authors: Leal, Raul A.; Bischof, Caroline; Lee, Youjin V.; Sawano, Shota; McAtee, Christopher C.; Latimer, Luke N.; Russ, Zachary N.; Dueber, John E.; Yu, Jin‐Quan; Sarpong, Richmond
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 39(2016)
• Page Start: 11824
• Page End: 11828
• Publication Date: 2016-08-29
• Subjects: C−H activation -- desymmetrization -- indole alkaloids -- indolization -- natural products; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201605475
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: We describe herein formal syntheses of the indole alkaloids cis ‐trikentrin A and herbindole B from a common meso ‐hydroquinone intermediate prepared by a ruthenium‐catalyzed [2+2+1+1] cycloaddition that has not been used previously in natural product synthesis. Key steps include a sterically demanding Buchwald–Hartwig amination as well as a unique C(sp 3 )−H amination/indole formation. Studies toward a selective desymmetrization of the meso ‐hydroquinone are also reported. Abstract : All of me(so) : A ruthenium‐catalyzed [2+2+1+1] cycloaddition provided a common meso ‐hydroquinone intermediate for formal syntheses of the indole alkaloids cis ‐trikentrin A and herbindole B (see scheme). Key steps of the synthesis include a sterically demanding Buchwald–Hartwig amination and an unprecedented C(sp 3 )−H amination/indolization reaction.