title: A Highly Stereoselective, Efficient, and Scalable Synthesis of the C(1)-C(9) Fragment of the Epothilones.
abstract: A second-generation synthesis of the C(1)-C(9) fragment of the epothilones is reported. The key tandem intramolecular silylformylation/crotylsilylation/"aprotic" Tamao oxidation sequence has been redeveloped as a stepwise intermolecular variant, allowing excellent levels of diastereoselectivity in the crotylation step and proceeds in 50% overall yield on gram scale. An improved synthesis of the homopropargyl alcohol starting material is also described, which proceeds in four steps and >99% ee from inexpensive starting materials and is amenable to multigram scales.
authors.affiliation: Department of Chemistry, Columbia University , 3000 Broadway, New York, New York 10027, United States.
authors.forename: Corinne N
authors.initials: CN
authors.lastname: Foley
authors.affiliation: Department of Chemistry, Columbia University , 3000 Broadway, New York, New York 10027, United States.
authors.forename: James L
authors.initials: JL
authors.lastname: Leighton
mesh_terms: D000438:Alcohols / Q000737:chemistry; D034261:Epothilones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D034261:Epothilones