Homolytic CαCβ Bond Cleavage in a Chiral Alkylarene Radical Cation: Effects of Asymmetric Microsolvation

Quantum Chemical Studies of Radical Cation Rearrangement, Radical Carbonylation, and Homolytic Substitution Reactions

Homolytic cleavage of the O-glycoside bond in carbohydrates: a steady-state radiolysis study.

The formation of products resulting from the O-glycoside bond cleavage following radiolysis of aqueous solutions of methyl-alpha-D-glucopyranoside (I), 3-O-methyl-alpha-D-glucopyranose (II), maltose, lactose, gentiobiose and cellobiose were studied. Radiation-induced destruction yields were also determined for dextran, laminarin and trimethylcelulose upon irradiation of their aqueous solutions....

Chiral metal nanoparticle-catalyzed asymmetric C-C bond formation reactions.

Chiral ligand-modified metal nanoparticles possess an attractive potential for application in asymmetric synthesis. This article focuses on chiral-nanoparticle-catalyzed asymmetric C-C bond formation reactions and discusses the nature of the active species.

Homolytic versus heterolytic dissociation of alkalimetal halides: the effect of microsolvation.

Herein we report density functional calculations of homolytic and heterolytic dissociation energies of the diatomic alkalimetal halides MX (M=Li, Na, K, Rb, and Cs and X=F, Cl, Br, I, and At) and their corresponding microsolvated structures MX(H(2)O)(n) (n=1 to 4). Our results show that the homolytic dissociation energy of the MX(H(2)O)(n) species increases with the number of water molecules in...

Anomalous C-C bond cleavage in sulfur-centered cation radicals containing a vicinal hydroxy group.

1,3-dithianyl cation radicals having alpha-hydroxy-neopentyl or similar groups in position 2, which are generated via oxidative photoinduced electron transfer, undergo anomalous fragmentation necessitating refinement of the accepted mechanism. Experimental and computational data support a rationale in which proton abstraction from the hydroxy group in the initial cation radical does not cause a...