title: Intramolecular Diels-Alder (IMDA) Studies toward the Synthesis of Australifungin. Stereocontrol in the Acetate Aldol Reaction of β,β'-Branched Aldehydes.
abstract: Studies of australifungin illustrate an enantiocontrolled synthesis of the trans-decalin core 28 via an intramolecular [4π + 2π] cycloaddition. This strategy utilizes the nitroalkene dienophile of 27 as a surrogate ketene equivalent. Stereocontrol at C-2 is critically important for an effective intramolecular Diels-Alder (IMDA) process. Our studies report high asymmetric induction using a nonracemic Duthaler titanium enolate in the acetate aldol reaction with β,β'-branched aldehyde 13 to introduce the required C-2 chirality.
authors.affiliation: Department of Chemistry, Indiana University , Bloomington, Indiana 47405, United States.
authors.forename: David R
authors.initials: DR
authors.lastname: Williams
authors.affiliation: Department of Chemistry, Indiana University , Bloomington, Indiana 47405, United States.
authors.forename: J Cullen
authors.initials: JC
authors.lastname: Klein
mesh_terms: D000085:Acetates / Q000737:chemistry; D000447:Aldehydes / Q000737:chemistry*; D061565:Cycloaddition Reaction; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry; D013237:Stereoisomerism; D013764:Tetrahydronaphthalenes / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000085:Acetates; D000447:Aldehydes; D009281:Naphthalenes; D013764:Tetrahydronaphthalenes; C094344:australifungin; C007229:decalin; C116609:3-hydroxybutanal