Organometallic enantiomeric scaffolding. A molybdenum-mediated intramolecular nucleophilic ketalization-demetalation cascade. Total synthesis of (+)-(1R,2S,5S,7R)-2-hydroxy-exo-brevicomin.
TpMo(CO)(2)(5-oxo-eta(3)-pyranyl) scaffolds bearing an internal alkoxide undergo a novel intramolecular nucleophilic ketalization reaction. The anionic intermediate is easily demetalated, rapidly providing the 6,8-dioxabicyclo[3.2.1]oct-3-en-2-one framework in moderate to good yields with high enantiopurity. An enantiocontrolled total synthesis of (+)-(1R,2S,5S,7R)-2-hydroxy-exo-brevicomin was accomplished utilizing the reaction sequence.
Cheng
Bo
B
Emory University, Department of Chemistry, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
Liebeskind
Lanny S
LS
D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D013237:Stereoisomerism
C544888:2-hydroxy-exo-brevicomin; D019086:Bridged Bicyclo Compounds, Heterocyclic; D008982:Molybdenum; C012219:brevicomin