A Density Functional Theory Study of the Enantioselective Reduction of Prochiral Ketones Promoted by Chiral Spiroborate Esters

作者：Wei Donghui; Tang Mingsheng^*; Zhang Wenjing; Zhao Jing; Sun Ling; Zhao Chufeng; Wang Homgming

来源：International Journal of Quantum Chemistry, 2011, 111(3): 596-605.

DOI：10.1002/qua.22307

• DFT
• mechanism
• chiral spiroborate esters

Recently, chiral spiroborate ester [(R)-2-((1,3,2-dioxaborolan-2- yloxy)methyl)pyrrolidine] has been experimentally employed as an effective chiral catalyst in the borane-mediated asymmetric reduction of prochiral ketones to produce the corresponding secondary alcohols. In this article, we have theoretically investigated the mechanism of the reduction using density functional theory. The results reveal that this reaction is accomplished via four steps. Fully geometry optimized reactants, products, transition states, and intermediates were obtained at the B3LYP/6-31G (d, p) level. The analysis of these results reveals one pathway that is more energetically favorable, and its associated geometries correlate well with the final products of the reaction. The further calculations show that the solvent effect of THF has no great influence on enantioselectivity of this reduction.

• 出版日期2011-3
• 单位郑州大学