149157-63-1Relevant academic research and scientific papers
Total Synthesis of (-)-Marinisporolide C
Dias, Luiz C.,De Lucca, Emilio C.
, p. 3019 - 3045 (2017/03/23)
The first total synthesis of (-)-marinisporolide C is described, which establishes unequivocally the relative and absolute configuration of this oxopolyene macrolide. Key features of this synthesis include a series of highly stereoselective aldol reactions followed by directed reductions to build the polyol domain, a Stille cross-coupling reaction to assemble the polyene, and an intramolecular Horner-Wadsworth-Emmons olefination to forge the macrocyclic ring. Despite the initial approach to marinisporolide A using a Yamaguchi macrolactonization reaction that was unsuccessful due to steric hindrance of the oxygen at the C33 position, we were able to prepare a known derivative of marinisporolide A and consequently confirm its stereochemical assignment.
Total Synthesis of the Oxopolyene Macrolide (-)-Marinisporolide C
Dias, Luiz C.,De Lucca, Emílio C.
supporting information, p. 6278 - 6281 (2016/01/09)
The first total synthesis of (-)-marinisporolide C was performed in 25 steps (longest linear sequence) and an overall yield of 1%. Due to the high degree of convergence and robustness, the C9-C35 fragment that corresponds to the polyol portion was obtaine
The exceptional chelating ability of dimethylaluminum chloride and methylaluminum dichloride. The merged stereochemical impact of α- and β-stereocenters in chelate-controlled carbonyl addition reactions with enolsilane and hydride nucleophiles
Evans,Allison,Yang,Masse
, p. 10840 - 10852 (2007/10/03)
A systematic investigation of the stereoselectivity in Lewis acid-promoted (Mukaiyama) aldol reactions of achiral unsubstituted enolsilanes and chiral β-hydroxy aldehydes proceeding under conditions favoring chelation control is presented. Good stereocontrol can be realized for enolsilane aldol reactions of β-alkoxy and β-silyloxy aldehydes bearing only an α- or a β-stereogenic center. Examination of the chelated intermediates for α,β-disubstituted aldehydes concludes that the syn aldehyde diastereomer possesses the arrangement of stereocenters wherein the α- and β-substituents impart a reinforcing facial bias upon the aldehyde carbonyl. Aldol reactions of syn aldehydes were thus observed to proceed with uniformly excellent diastereofacial selectivity. Aldol reactions of the corresponding anti aldehydes containing opposing stereocontrol elements at the α- and β-positions exhibit variable and unpredictable selectivity.
