Indolyne and Aryne Distortions and Nucleophilic Regioselectivites

作者：Paul H.-Y. Cheong, Robert S. Paton, Sarah M. Bronner, G-Yoon Jamie Im, Neil K. Garg, K. N. Houk · 发表于：Journal of the American Chemical Society · 年份：2010 · DOI：10.1021/ja9098643 · 被引用次数：249 · 研究领域：Cyclization and Aryne Chemistry、Catalytic Alkyne Reactions、Organic Chemistry Cycloaddition Reactions

Density functional theory computations reproduce the surprisingly high regioselectivities in nucleophilic additions and cycloadditions to 4,5-indolynes and the low regioselectivities in the reactions of 5,6-indolynes. Transition-state distortion energies control the regioselectivities, activating the 5 and 6 positions over the 4 and 7 positions, leading to high preferences for 5- and 6-substituted products from 4,5- and 6,7-indolynes, respectively. Orbital and electrostatic interactions have only minor effects, producing low regioselectivities in the reactions of 5,6-indolynes. The distortion model predicts high regioselectivities with 6,7-indolynes; these have been verified experimentally. The regioselectivities found with other arynes are explained on the basis of distortion energies that are reflected in reactant geometries.