Regioselectivity in the palladium-catalyzed addition of carbon nucleophiles to carbocyclic derivatives.
The regioselectivity of Pd-catalyzed malonate additions and arylations to cycloalkenyl esters can be predicted by completing a stereochemical analysis of the Pd-pi-allyl complex. The Pd-catalyzed malonate additions which have the greatest degree of regioselectivity are in which substituents have a steric influence in blocking the incoming nucleophile. Cyclopentenyl substrates displayed lower regioselectivity than the cyclohexyl counterparts presumably due to increased planarity of the system. Arylations using tin and hypervalent silicon reagents were compared.
Hoke
Molly E
ME
Department of Chemistry and Biochemistry, The University of Maryland, College Park 20742, USA.
Brescia
Marc-Raleigh
MR
Bogaczyk
Suzanne
S
DeShong
Philip
P
King
Bryan W
BW
Crimmins
Michael T
MT
D001565:Benzoates / Q000138:chemical synthesis* / Q000737:chemistry*; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D018360:Crystallography, X-Ray; D003500:Cyclization; D003510:Cyclohexanes / Q000737:chemistry; D003517:Cyclopentanes / Q000737:chemistry; D004952:Esters / Q000138:chemical synthesis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008314:Malonates / Q000737:chemistry; D013058:Mass Spectrometry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D012825:Silicon / Q000737:chemistry; D013237:Stereoisomerism; D014001:Tin / Q000737:chemistry
D001565:Benzoates; D019086:Bridged Bicyclo Compounds, Heterocyclic; D003510:Cyclohexanes; D003517:Cyclopentanes; D004952:Esters; D008314:Malonates; D009942:Organometallic Compounds; D010165:Palladium; D014001:Tin; D012825:Silicon