Stepwise Mechanism for the Bromination of Arenes by a Hypervalent Iodine Reagent

Albert Granados; Alexandr Shafir; Ana Arrieta; Fernando P. Cossío; Adelina Vallribera

doi:10.1021/acs.joc.9b02784

Stepwise Mechanism for the Bromination of Arenes by a Hypervalent Iodine Reagent

Albert Granados, Alexandr Shafir, Ana Arrieta, Fernando P. Cossío, Adelina Vallribera

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Abstract

A mild, metal-free bromination method of arenes has been developed using the combination of bis(trifluoroacetoxy)iodobencene and trimethylsilyl bromide. In situ-formed dibromo(phenyl)-λ3-iodane (PhIBr2) is proposed as the reactive intermediate. This methodology using PIFA/TMSBr has been applied with success to a great number of substrates (25 examples). The treatment of mono-substituted activated arenes led to para-brominated products (2u–z) in excellent 83–96% yields. Density functional theory calculations indicate a stepwise mechanism involving a double bromine addition followed by a type II dyotropic reaction with concomitant re-aromatization of the six-membered ring.

Original language	English
Pages (from-to)	2142
Number of pages	2150
Journal	The Journal Of Organic Chemistry
Volume	85
Issue number	4
DOIs	https://doi.org/10.1021/acs.joc.9b02784
Publication status	Published - 21 Feb 2020

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title = "Stepwise Mechanism for the Bromination of Arenes by a Hypervalent Iodine Reagent",

abstract = "A mild, metal-free bromination method of arenes has been developed using the combination of bis(trifluoroacetoxy)iodobencene and trimethylsilyl bromide. In situ-formed dibromo(phenyl)-λ3-iodane (PhIBr2) is proposed as the reactive intermediate. This methodology using PIFA/TMSBr has been applied with success to a great number of substrates (25 examples). The treatment of mono-substituted activated arenes led to para-brominated products (2u–z) in excellent 83–96% yields. Density functional theory calculations indicate a stepwise mechanism involving a double bromine addition followed by a type II dyotropic reaction with concomitant re-aromatization of the six-membered ring.",

author = "Albert Granados and Alexandr Shafir and Ana Arrieta and Coss{\'i}o, {Fernando P.} and Adelina Vallribera",

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T1 - Stepwise Mechanism for the Bromination of Arenes by a Hypervalent Iodine Reagent

AU - Granados, Albert

AU - Shafir, Alexandr

AU - Arrieta, Ana

AU - Cossío, Fernando P.

AU - Vallribera, Adelina

PY - 2020/2/21

Y1 - 2020/2/21

N2 - A mild, metal-free bromination method of arenes has been developed using the combination of bis(trifluoroacetoxy)iodobencene and trimethylsilyl bromide. In situ-formed dibromo(phenyl)-λ3-iodane (PhIBr2) is proposed as the reactive intermediate. This methodology using PIFA/TMSBr has been applied with success to a great number of substrates (25 examples). The treatment of mono-substituted activated arenes led to para-brominated products (2u–z) in excellent 83–96% yields. Density functional theory calculations indicate a stepwise mechanism involving a double bromine addition followed by a type II dyotropic reaction with concomitant re-aromatization of the six-membered ring.

AB - A mild, metal-free bromination method of arenes has been developed using the combination of bis(trifluoroacetoxy)iodobencene and trimethylsilyl bromide. In situ-formed dibromo(phenyl)-λ3-iodane (PhIBr2) is proposed as the reactive intermediate. This methodology using PIFA/TMSBr has been applied with success to a great number of substrates (25 examples). The treatment of mono-substituted activated arenes led to para-brominated products (2u–z) in excellent 83–96% yields. Density functional theory calculations indicate a stepwise mechanism involving a double bromine addition followed by a type II dyotropic reaction with concomitant re-aromatization of the six-membered ring.

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DO - 10.1021/acs.joc.9b02784

M3 - Article

SN - 0022-3263

VL - 85

SP - 2142

JO - The Journal Of Organic Chemistry

JF - The Journal Of Organic Chemistry

IS - 4

ER -

Stepwise Mechanism for the Bromination of Arenes by a Hypervalent Iodine Reagent

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