Theoretical Bond Dissociation Energies of Halo-Heterocycles: Trends and Relationships to Regioselectivity in Palladium-Catalyzed Cross-Coupling Reactions

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• 作者：Yeimy Garcia ; Franziska Schoenebeck ; Claude Y. Legault ; Craig A. Merlic ; K. N. Houk
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：May 13, 2009
• 年：2009
• 卷：131
• 期：18
• 页码：6632-6639
• 全文大小：299K
• 年卷期：v.131,no.18(May 13, 2009)
• ISSN：1520-5126

文摘

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 π* (LUMO) and PdL₂ 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.