Mechanistic studies on Au(I)-catalyzed [3,3]-sigmatropic rearrangements using cyclopropane probes.
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.
Mauleón
Pablo
P
Department of Chemistry, University of California, Berkeley, California 94720, USA.
Krinsky
Jamin L
JL
Toste
F Dean
FD
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*
D000498:Allyl Compounds; D003521:Cyclopropanes; D004952:Esters; D014753:Vinyl Compounds; C100195:vinyl ether; D006046:Gold; C030797:cyclopropane