Dual role of carboxylic acid additive: Mechanistic studies and implication for the asymmetric C-H amidation Dedicated to Professor Yoshiaki Nakao on his receipt of the Tetrahedron Young Investigator Award

Donghyeon Gwon; Sehoon Park; Sukbok Chang

doi:10.1016/j.tet.2015.02.065

Dual role of carboxylic acid additive: Mechanistic studies and implication for the asymmetric C-H amidation Dedicated to Professor Yoshiaki Nakao on his receipt of the Tetrahedron Young Investigator Award

Donghyeon Gwon, Sehoon Park, Sukbok Chang^*

^*Corresponding author for this work

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

85 Scopus citations

Abstract

Acid additive effects in the Ir-catalyzed C-H amidation of arylphosphoryl compounds were examined. Structure of catalytically active metal species was elucidated: mono-cationic iridium catalyst [Cp^∗Ir(III)(OAc)](NTf₂) being mainly responsible for the C-H bond activation. Mechanistic studies revealed a dual role of carboxylic acid additive operating both in the generation of an iridacyclic intermediate and in the protodemetalation process to release amidated products. The fact that asymmetric C-H amidation was achieved albeit in moderate enantioselectivity by using chiral carboxylic acid supports our proposal especially with regard to the role of acid additive.

Original language	English
Pages (from-to)	4504-4511
Number of pages	8
Journal	Tetrahedron
Volume	71
Issue number	26-27
DOIs	https://doi.org/10.1016/j.tet.2015.02.065
State	Published - 30 May 2015
Externally published	Yes

Keywords

Acid additive effects
Asymmetric induction
C-H amidation
Mechanistic study
Phosphoryl compounds

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10.1016/j.tet.2015.02.065

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title = "Dual role of carboxylic acid additive: Mechanistic studies and implication for the asymmetric C-H amidation Dedicated to Professor Yoshiaki Nakao on his receipt of the Tetrahedron Young Investigator Award",

abstract = "Acid additive effects in the Ir-catalyzed C-H amidation of arylphosphoryl compounds were examined. Structure of catalytically active metal species was elucidated: mono-cationic iridium catalyst [Cp∗Ir(III)(OAc)](NTf2) being mainly responsible for the C-H bond activation. Mechanistic studies revealed a dual role of carboxylic acid additive operating both in the generation of an iridacyclic intermediate and in the protodemetalation process to release amidated products. The fact that asymmetric C-H amidation was achieved albeit in moderate enantioselectivity by using chiral carboxylic acid supports our proposal especially with regard to the role of acid additive.",

keywords = "Acid additive effects, Asymmetric induction, C-H amidation, Mechanistic study, Phosphoryl compounds",

author = "Donghyeon Gwon and Sehoon Park and Sukbok Chang",

year = "2015",

month = may,

day = "30",

doi = "10.1016/j.tet.2015.02.065",

language = "英语",

volume = "71",

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Dual role of carboxylic acid additive: Mechanistic studies and implication for the asymmetric C-H amidation Dedicated to Professor Yoshiaki Nakao on his receipt of the Tetrahedron Young Investigator Award. / Gwon, Donghyeon; Park, Sehoon; Chang, Sukbok.
In: Tetrahedron, Vol. 71, No. 26-27, 30.05.2015, p. 4504-4511.

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

TY - JOUR

T1 - Dual role of carboxylic acid additive

T2 - Mechanistic studies and implication for the asymmetric C-H amidation Dedicated to Professor Yoshiaki Nakao on his receipt of the Tetrahedron Young Investigator Award

AU - Gwon, Donghyeon

AU - Park, Sehoon

AU - Chang, Sukbok

PY - 2015/5/30

Y1 - 2015/5/30

N2 - Acid additive effects in the Ir-catalyzed C-H amidation of arylphosphoryl compounds were examined. Structure of catalytically active metal species was elucidated: mono-cationic iridium catalyst [Cp∗Ir(III)(OAc)](NTf2) being mainly responsible for the C-H bond activation. Mechanistic studies revealed a dual role of carboxylic acid additive operating both in the generation of an iridacyclic intermediate and in the protodemetalation process to release amidated products. The fact that asymmetric C-H amidation was achieved albeit in moderate enantioselectivity by using chiral carboxylic acid supports our proposal especially with regard to the role of acid additive.

AB - Acid additive effects in the Ir-catalyzed C-H amidation of arylphosphoryl compounds were examined. Structure of catalytically active metal species was elucidated: mono-cationic iridium catalyst [Cp∗Ir(III)(OAc)](NTf2) being mainly responsible for the C-H bond activation. Mechanistic studies revealed a dual role of carboxylic acid additive operating both in the generation of an iridacyclic intermediate and in the protodemetalation process to release amidated products. The fact that asymmetric C-H amidation was achieved albeit in moderate enantioselectivity by using chiral carboxylic acid supports our proposal especially with regard to the role of acid additive.

KW - Acid additive effects

KW - Asymmetric induction

KW - C-H amidation

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DO - 10.1016/j.tet.2015.02.065

M3 - 文章

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SN - 0040-4020

VL - 71

SP - 4504

EP - 4511

JO - Tetrahedron

JF - Tetrahedron

IS - 26-27

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Dual role of carboxylic acid additive: Mechanistic studies and implication for the asymmetric C-H amidation Dedicated to Professor Yoshiaki Nakao on his receipt of the Tetrahedron Young Investigator Award

Abstract

Keywords

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