Catalytic and regioselective ring expansion of arylcyclobutanones with trimethylsilyldiazomethane. Ligand-dependent entry to beta-ketosilane or enolsilane adducts.
Divergent reactivity is uncovered in the homologation of arylcyclobutanones with trimethylsilyldiazomethane. With Sc(OTf)(3) as catalyst, enolsilanes are obtained with a high preference for methylene migration. By contrast, Sc(hfac)(3) gives beta-ketosilanes with both regio- and diastereocontrol. Each adduct affords the cyclopentanone upon hydrolysis.
Dabrowski
Jennifer A
JA
Department of Chemistry, Eugene F. Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Moebius
David C
DC
Wommack
Andrew J
AJ
Kornahrens
Anne F
AF
Kingsbury
Jason S
JS
D002384:Catalysis; D020650:Combinatorial Chemistry Techniques; D003517:Cyclopentanes / Q000138:chemical synthesis* / Q000737:chemistry; D003978:Diazomethane / Q000031:analogs & derivatives* / Q000737:chemistry; D008024:Ligands; D015394:Molecular Structure; D013237:Stereoisomerism; D014297:Trimethylsilyl Compounds / Q000737:chemistry*
D003517:Cyclopentanes; D008024:Ligands; D014297:Trimethylsilyl Compounds; C007201:cyclopentanone; D003978:Diazomethane; C060070:trimethylsilyldiazomethane