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• W1964225536 endingPage "1847" @default.
• W1964225536 startingPage "1842" @default.
• W1964225536 abstract "The first highly selective C−H chlorination, bromination, and iodination of cubane (1) utilizing polyhalomethanes as halogen sources under phase-transfer (PT) conditions is described. Isomeric dihalocubanes with all possible combinations of chlorine, bromine, and iodine in ortho, meta, and para positions were also prepared by this method; m-dihalo products form preferentially. Ab initio and density functional theory (DFT) computations were used to rationalize the pronounced differences in the reactions of 1 with halogen (Hal•) vs carbon-centered trihalomethyl (Hal3C•) radicals (Hal = Cl, Br). For Hal3C radicals the C−H abstraction pathway is less unfavorable (ΔG‡298 = 21.6 kcal/mol for Cl3C• and 19.4 kcal/mol for Br3C• at B3LYP/6-311+G**//B3LYP/6-31G**) than the fragmentation of the cubane skeleton via SH2-attack on one of the carbon atoms of 1 (ΔG‡298 = 33.8 and 35.1 kcal/mol, respectively). In stark contrast, the reaction of 1 with halogen atoms preferentially follows the fragmentation pathway (ΔG‡298 = 2.1 and 7.5 kcal/mol) and C−H abstraction is more unfavorable (ΔG‡298 = 4.6 and 12.0 kcal/mol). Our computational results nicely agree with the behavior of 1 under PT halogenation conditions (where Hal3C• is involved in the activation step) and under free-radical photohalogenation with Hal2 (Della, E. W., et al. J. Am. Chem. Soc. 1992, 114, 10730). The incorporation of a second halogen atom preferentially in the meta position of halocubanes demonstrates the control of the regioselectivity by molecular orbital symmetry." @default.
• W1964225536 created "2016-06-24" @default.
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• W1964225536 date "2001-02-13" @default.
• W1964225536 modified "2023-10-11" @default.
• W1964225536 title "Halogenation of Cubane under Phase-Transfer Conditions: Single and Double C−H-Bond Substitution with Conservation of the Cage Structure" @default.
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• W1964225536 doi "https://doi.org/10.1021/ja0032677" @default.
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