title: Mechanistic studies on Au(I)-catalyzed [3,3]-sigmatropic rearrangements using cyclopropane probes.
abstract: A comparative study of the Au(I)-catalyzed [3,3]-sigmatropic rearrangement of propargylic esters and propargyl vinyl ethers is described. Stereochemically defined cyclopropanes are employed as mechanistic probes to provide new synthetic and theoretical data concerning the reversibility of this type of rearrangement. Factors controlling the structure-reactivity relationship of Au(I)-coordinated allenes have been examined, thereby allowing for controlled access to orthogonal reactivity.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA.
authors.forename: Pablo
authors.initials: P
authors.lastname: Mauleón
authors.forename: Jamin L
authors.initials: JL
authors.lastname: Krinsky
authors.forename: F Dean
authors.initials: FD
authors.lastname: Toste
mesh_terms: D000498:Allyl Compounds; D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods; D003521:Cyclopropanes / Q000737:chemistry*; D004952:Esters / Q000737:chemistry; D006046:Gold / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D013816:Thermodynamics; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D000498:Allyl Compounds; D003521:Cyclopropanes; D004952:Esters; D014753:Vinyl Compounds; C100195:vinyl ether; D006046:Gold; C030797:cyclopropane