Total Synthesis of (−)-Reveromycin A

Abstract

The asymmetric total synthesis of (-)-reveromycin A is described. The key steps involved a Lewis acid catalyzed inverse electron demand hetero-Diels-Alder reaction followed by hydroboration/oxidation to afford the spiroketal core 4 in a highly stereoselective manner and introduction of the C18 hemisuccinate by high-pressure acylation.

Chemical and Enzymatic Approaches to Carbohydrate-Derived Spiroketals: Di-D-Fructose Dianhydrides (DFAs)

“…Di- d -fructose dianhydrides (DFAs) comprise a diverse family of mono- or dispirocyclic acetals obtained by condensation of two fructose molecules, with formation of two reciprocal glycosidic linkages. Their basic mono- or bis-spiroketal framework resembles that found in many relevant natural products, including steroidal saponins, polyether ionophores, macrolide antibiotics, insect pheromones, and toxic metabolites from algae and fungi [ 1 , 2 , 3 , 4 , 5 ], and is the target of much synthetic effort [ 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 ]. DFAs are formed upon thermal and/or acidic activation of sucrose- and/or d -fructose-rich materials.…”

Synthesis of 5,6- and 6,6-Spirocyclic Compounds

“…The hetero-Diels-Alder reaction (HDA) has been used extensively for the construction of spiroacetals [4], notably in the synthesis of the reveromycins [150][151][152][153]. In particular, the recent development of mild methods for the generation of ortho-quinone methides (o-QM) in the presence of sensitive five-membered exocyclic enol ethers has revealed an alternative route to benzannulated 5,6-spiroacetals.…”

Synthesis, X‐ray Analysis, and Biological Activities of Novel Oxazolidinethiones

“…The increasing availability of enantiopure vic ‐aminoalcohols has stimulated interest in developing chemistry, which makes use of oxazolidinone/oxazolidinthiones . Oxazolidinethiones have been used synthetically in other ways, primarily as chiral auxiliaries , but also as intermediates in the synthesis of enantiopure protected aryl‐ β ‐hydroxyl‐ α ‐amino acids and 1‐( Boc )‐amino‐1‐alkenylphosphonate esters , as a derivative for kinetic resolutions , as pseudo‐C‐nucleosides , in radical reactions , and as precursors for other oxazolidines . Carbon disulfide , thiophosgene , or bis(imidazolyl)thione have been used to prepare them from the corresponding amino alcohols, as well as hydroxide addition to isothiocyanates and cycloaddition of aldehydes to anions of substituted methyl isothiocyanates .…”