title: Design, development, mechanistic elucidation, and rational optimization of a tandem Ireland Claisen/Cope rearrangement reaction for rapid access to the (iso)cyclocitrinol core.
abstract: An approach to the synthesis of the (iso)cyclocitrinol core structure is described. The key step is a tandem Ireland Claisen/Cope rearrangement sequence, wherein the Ireland Claisen rearrangement effects ring contraction to a strained 10-membered ring, and that strain in turn drives the Cope rearrangement under unusually mild thermal conditions. A major side product was identified as resulting from an unexpected and remarkably facile [1,3]-sigmatropic rearrangement, and a tactic to disfavor the [1,3] pathway and increase the efficiency of the tandem reaction was rationally devised.
authors: Department of Chemistry, Columbia University , NewYork, New York 10027, United States.
authors: Christopher W
authors: CW
authors: Plummer
authors: Carolyn S
authors: CS
authors: Wei
authors: Carrie E
authors: CE
authors: Yozwiak
authors: Arash
authors: A
authors: Soheili
authors: Sara O
authors: SO
authors: Smithback
authors: James L
authors: JL
authors: Leighton
mesh_terms: D007783:Lactones / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism; D013729:Terpenes / Q000138:chemical synthesis*
chemical_list: D007783:Lactones; D013729:Terpenes; C412874:cyclocitrinol