A Twist of the Twist Mechanism, 2-Iodoxybenzoic Acid (IBX)-Mediated Oxidation of Alcohol Revisited: Theory and Experiment

作者：Jiang, Heming; Sun, Tian-Yu; Wang, Xiao; Xie, Yaoming; Zhang, Xinhao^*; Wu, Yun-Dong^*; Schaefer, Henry F., III^*

来源：Organic Letters, 2017, 19(24): 6502-6505.

DOI：10.1021/acs.orglett.7b03167

• O-IODOXYBENZOIC ACID
• HYPERVALENT IODINE COMPOUNDS
• MOLECULAR WAVE-FUNCTIONS
• POLYVALENT IODINE
• SELECTIVE OXIDATION
• BENCHMARK CALCULATIONS
• DENSITY FUNCTIONALS
• ORGANIC-CHEMISTRY
• BASIS-SETS
• REAGENTS

2-Iodoxybenzoic acid (IBX) is an important species for the oxidation of alcohols to aldehydes or ketones. An often-cited mechanism involving a hypervalent twist as the rate-determining step (RDS) is inconsistent with kinetic isotope effect (KIE) experiments. The computations with larger basis sets reveal that the reductive elimination involving the C-H bond cleavage is the RDS (rate-determining step). Further computational/experimental studies suggest that the reactivity can be improved by adjusting the trans influence with Lewis acids.

• 出版日期2017-12-15
• 单位北京大学; 北京大学深圳研究生院