Expeditious Synthesis of Enantioenriched Tetrahydropyrans via Chemoselective C−N bond Cleavage of Aza‐Oxa‐Bicyclo[3.2.1]Octanes. Issue 20 (17th August 2017)

• Record Type: Journal Article
• Authors: D'Elia, Cecilia Sasso; Goudedranche, Sébastien; Constantieux, Thierry; Bella, Marco; Bonne, Damien; Rodriguez, Jean
• Is Part Of: Advanced synthesis & catalysis. Volume 359:Issue 20(2017)
• Page Start: 3638
• Page End: 3641
• Publication Date: 2017-08-17
• Subjects: Tetrahydropyrans -- Azepanes -- Organocatalysis -- Multiple bond-forming transformations -- Oxocarbenium ions; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201700735
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: A rapid synthesis of enantioenriched 2, 3, 4‐trisubstituted tetrahydropyrans in good yields and stereoselectivities is reported. The first step is a domino organocatalytic reaction between ambident electrophilic and 1, 4‐bis‐nucleophilic 1, 2‐ketoamides and 1, 3‐bis‐electrophilic enals, leading to aza‐oxa‐bicyclo[3.2.1]octane. Then, the TiCl4 /Et3 SiH system ensures a chemoselective cleavage of the C−N bond and affords the desired trisubstituted tetrahydropyran in good yield and with conservation of the precursors optical purity. This final synthetic operation includes two consecutive oxocarbenium ion formation and reductions. Abstract :