Effects of Chemical Structure on the Thermodynamic Efficiency of Radical Chain Carriers for Organic Synthesis

• Published in: Journal of organic chemistry Vol. 76; no. 6; pp. 1715 - 1726
• Main Authors: Lin, Ching Yeh, Peh, Jessie, Coote, Michelle L
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 18.03.2011
• Subjects: Chemistry; Exact sciences and technology; Free radicals chemistry; Kinetics and mechanisms; Organic chemistry; Reactivity and mechanisms; Solvent effect; Dehalogenation; Chemical bond; Chemical structure; Theoretical study; Organic bromine compounds; Hydrides; Reducing agent; Organic chlorine compounds; Dissociation energy; Free energy; Organic halogen compounds; Optimization; Organic synthesis; Thermodynamics; Organic free radical; Bismuth; Tin; Boron Organic compounds; Organic borane; Kinetics; Inclusion compound; Moller Plesset partition; Electron donor
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo102368v

The chain carrier index (CCI), defined as the ratio of the bond dissociation free energies (BDFE) of corresponding chain carrier halides and hydrides, is proposed as a measure of the thermodynamic efficiency of chain carriers for radical dehalogenation. The larger this value is relative to the corresponding value of the organic substrate, the more thermodynamically efficient the process. The chloride and bromide CCIs were evaluated at the G3(MP2)-RAD(+) level of theory for 120 different R-groups, covering a broad range of carbon-centered and noncarbon-centered species; the effects of solvent and temperature have also been studied. The broad finding from this work is that successful chain carriers generally maximize the strength of their halide (versus hydride bonds) through charge-shift bonding. As a result, the thermodynamic efficiency of a chain carrier tends to increase down the periodic table, and also with the inclusion of stronger electron donating substituents. The CCIs of carbon-centered species fall into a relatively narrow range so that, even when the CCI is maximized through inclusion of lone pair donor OMe or NMe2 groups, the thermodynamic driving force for dehalogenation of other organic substrates is modest at best, and the process is likely to be kinetically hampered. Among the noncarbon-centered species studied, bismuth- and borane-centered compounds have some of the highest CCI values and, although their kinetics requires further optimization, these classes of compounds would be worth further investigation as tin-free radical reducing agents.