Theoretical bond dissociation energies of halo-heterocycles: trends and relationships to regioselectivity in palladium-catalyzed cross-coupling reactions.
Selectivity of the palladium-catalyzed cross-coupling reactions of heterocycles bearing multiple identical halogens is mainly determined by the relative ease of oxidative addition. This is related to both the energy to distort the carbon halogen bond to the transition-state geometry (related to the CX bond-dissociation energy) and to the interaction between the heterocycle pi* (LUMO) and PdL(2) HOMO (J. Am. Chem. Soc. 2007, 129, 12664). The computed bond dissociation energies of a larger series of halo-heterocycles have been explored with B3LYP and higher accuracy G3B3 calculations. Quantitative trends in bond dissociation energies have been identified for five- and six-membered chloro and bromo substituted heterocycles with N, O, and S heteroatoms.
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
Yeimy
Y
Garcia
Franziska
F
Schoenebeck
Claude Y
CY
Legault
Craig A
CA
Merlic
K N
KN
Houk
D002384:Catalysis; D003432:Cross-Linking Reagents / Q000737:chemistry; D006219:Halogens / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry*; D008956:Models, Chemical; D008962:Models, Theoretical; D010165:Palladium
D003432:Cross-Linking Reagents; D006219:Halogens; D006571:Heterocyclic Compounds; D010165:Palladium