Total synthesis of gabosines via an iron-catalyzed intramolecular tandem aldol process

• Published in: Tetrahedron Vol. 67; no. 48; pp. 9305 - 9310
• Main Authors: Mac, Dinh Hung, Samineni, Ramesh, Sattar, Abdul, Chandrasekhar, Srivari, Yadav, Jhillu Singh, Grée, René
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 02.12.2011; Elsevier
• Subjects: Aldehydes; Aldolisation; Alicyclic compounds; Alicyclic compounds, terpenoids, prostaglandins, steroids; Carbohydrates with 4, 5, 6, ... C atoms, dissacharides and oligosaccharides; Carbohydrates. Nucleosides and nucleotides; Chemical Sciences; Chemistry; Chemistry, Organic; Compatibility; Cyclohexanone; Cyclohexenone; Derivatives; Exact sciences and technology; Gabosine; Iron pentacarbonyl; Natural products; Noncondensed benzenic compounds; Organic chemistry; Physical Sciences; Precursors; Preparations and properties; Science & Technology; Stereochemistry; Synthesis (chemistry); Tetrahedrons; Cyclohexenone; Gabosine; Iron pentacarbonyl; Natural products; Aldolisation; ENANTIOSELECTIVE SYNTHESIS; CARBA-SUGARS; STREPTOMYCES; HIYAMA-KISHI REACTION; ALLYLIC ALCOHOLS; (-)-GABOSINE; CONDENSATION; STEREOSELECTIVE-SYNTHESIS; KEY-STEP; DERIVATIVES; Transition element complexes; Iron; Mannose; Glucose; Stereochemistry; Aldol condensation; Cyclohexanone derivative; Benzylic compound; Vinylic compound; Cyclohexenone derivative; Polyol; Chemical synthesis; Ferrier rearrangement; Intramolecular reaction; Protecting group; Catalytic reaction; Aldose; Oside; Transition metal Carbonyl Complexes; Transition metal; Natural compound; Tandem reaction; Total synthesis; Iron Carbonyl Complexes; Galactose
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2011.09.121

Several gabosines, belonging to polyhydroxy-cyclohexenone and cyclohexanone class of natural products, are synthesized in various stereoforms using an intramolecular iron-catalyzed tandem aldol process. The reaction, which starts from vinylic pyranoses, is compatible with two different OH protecting groups (acetyl and benzyl). Further, like the Ferrier carbocyclisation, it is not sensitive to the stereochemistry of sugar molecules used as precursors: six different gabosine-type molecules have been prepared by this route starting from d-Glucose, d-Mannose, and d-Galactose derivatives. Similar reactions were performed from d-Galactose and d-Glucose [Display omitted]