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

Heming Jiang; Tian Yu Sun; Xiao Wang; Yaoming Xie; Xinhao Zhang; Yun Dong Wu; Henry F. Schaefer

doi:10.1021/acs.orglett.7b03167

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

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

^*Corresponding author for this work

Research output: Contribution to journal › Journal Article › peer-review

38 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	6502-6505
Number of pages	4
Journal	Organic Letters
Volume	19
Issue number	24
DOIs	https://doi.org/10.1021/acs.orglett.7b03167
Publication status	Published - 15 Dec 2017
Externally published	Yes

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© 2017 American Chemical Society.

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abstract = "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.",

author = "Heming Jiang and Sun, \{Tian Yu\} and Xiao Wang and Yaoming Xie and Xinhao Zhang and Wu, \{Yun Dong\} and Schaefer, \{Henry F.\}",

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AU - Jiang, Heming

AU - Sun, Tian Yu

AU - Wang, Xiao

AU - Xie, Yaoming

AU - Zhang, Xinhao

AU - Wu, Yun Dong

AU - Schaefer, Henry F.

PY - 2017/12/15

Y1 - 2017/12/15

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AB - 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.

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JF - Organic Letters

IS - 24

ER -

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

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