Developments in the Reactivity of 2-Methylimidazolium Salts

Daniela Peixoto; Margarida Figueiredo; Manoj B. Gawande; Marta C Corvo; Gerd Vanhoenacker; Carlos A M Afonso; Luisa M Ferreira; Paula S. Branco

doi:10.1021/acs.joc.7b00807

Developments in the Reactivity of 2-Methylimidazolium Salts

Daniela Peixoto, Margarida Figueiredo, Manoj B. Gawande, Marta C Corvo, Gerd Vanhoenacker, Carlos A M Afonso, Luisa M Ferreira, Paula S. Branco

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

6 Citations (Scopus)

Abstract

Unexpected and unusual reactivity of 2-methylimidazolium salts toward aryl-N-sulfonylimines and aryl aldehydes is here reported. Upon reaction with aryl-N-sulfonylimines, the addition product, arylethyl-2-imidazolium-1-tosylamide (3), is formed with moderate to good yields, while upon reaction with aldehydes, the initial addition product (6) observed in NMR and HPLC-MS experimental analysis is postulated by us as an intermediate to the final conversion to carboxylic acids. Studies in the presence and absence of molecular oxygen allow us to conclude that the imidazolium salts is crucial for the oxidation. A detailed mechanistic study was carried out to provide insights regarding this unexpected reactivity.

Original language	English
Pages (from-to)	6232-6241
Number of pages	10
Journal	Journal of Organic Chemistry
Volume	82
Issue number	12
DOIs	https://doi.org/10.1021/acs.joc.7b00807
Publication status	Published - 16 Jun 2017

Keywords

N-HETEROCYCLIC CARBENES
C BOND-CLEAVAGE
VITRO ANTITUMOR-ACTIVITY
IONIC LIQUIDS
ENZOIN CONDENSATION
EFFICIENT
CATALYSIS
ALDEHYDES
DESIGN
TRANSFORMATIONS

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title = "Developments in the Reactivity of 2-Methylimidazolium Salts",

abstract = "Unexpected and unusual reactivity of 2-methylimidazolium salts toward aryl-N-sulfonylimines and aryl aldehydes is here reported. Upon reaction with aryl-N-sulfonylimines, the addition product, arylethyl-2-imidazolium-1-tosylamide (3), is formed with moderate to good yields, while upon reaction with aldehydes, the initial addition product (6) observed in NMR and HPLC-MS experimental analysis is postulated by us as an intermediate to the final conversion to carboxylic acids. Studies in the presence and absence of molecular oxygen allow us to conclude that the imidazolium salts is crucial for the oxidation. A detailed mechanistic study was carried out to provide insights regarding this unexpected reactivity.",

keywords = "N-HETEROCYCLIC CARBENES, C BOND-CLEAVAGE, VITRO ANTITUMOR-ACTIVITY, IONIC LIQUIDS, ENZOIN CONDENSATION, EFFICIENT, CATALYSIS, ALDEHYDES, DESIGN, TRANSFORMATIONS",

author = "Daniela Peixoto and Margarida Figueiredo and Gawande, {Manoj B.} and Corvo, {Marta C} and Gerd Vanhoenacker and Afonso, {Carlos A M} and Ferreira, {Luisa M} and Branco, {Paula S.}",

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year = "2017",

month = jun,

day = "16",

doi = "10.1021/acs.joc.7b00807",

language = "English",

volume = "82",

pages = "6232--6241",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "ACS - American Chemical Society",

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AU - Peixoto, Daniela

AU - Figueiredo, Margarida

AU - Gawande, Manoj B.

AU - Corvo, Marta C

AU - Vanhoenacker, Gerd

AU - Afonso, Carlos A M

AU - Ferreira, Luisa M

AU - Branco, Paula S.

N1 - Sem PDF. Associated Laboratory for Sustainable Chemistry - Clean Processes and Technogies LAQV ERDF (POCI-01-0145-FEDER-007265) Fundacao para a Ciencia e Tecnologia (RECI/BBB-BQB/0230/2012) Ministry of Education, Youth and Sports of the Czech Republic (LO1305) FCT/MEC(UID/QUI/50006/2013)

PY - 2017/6/16

Y1 - 2017/6/16

N2 - Unexpected and unusual reactivity of 2-methylimidazolium salts toward aryl-N-sulfonylimines and aryl aldehydes is here reported. Upon reaction with aryl-N-sulfonylimines, the addition product, arylethyl-2-imidazolium-1-tosylamide (3), is formed with moderate to good yields, while upon reaction with aldehydes, the initial addition product (6) observed in NMR and HPLC-MS experimental analysis is postulated by us as an intermediate to the final conversion to carboxylic acids. Studies in the presence and absence of molecular oxygen allow us to conclude that the imidazolium salts is crucial for the oxidation. A detailed mechanistic study was carried out to provide insights regarding this unexpected reactivity.

AB - Unexpected and unusual reactivity of 2-methylimidazolium salts toward aryl-N-sulfonylimines and aryl aldehydes is here reported. Upon reaction with aryl-N-sulfonylimines, the addition product, arylethyl-2-imidazolium-1-tosylamide (3), is formed with moderate to good yields, while upon reaction with aldehydes, the initial addition product (6) observed in NMR and HPLC-MS experimental analysis is postulated by us as an intermediate to the final conversion to carboxylic acids. Studies in the presence and absence of molecular oxygen allow us to conclude that the imidazolium salts is crucial for the oxidation. A detailed mechanistic study was carried out to provide insights regarding this unexpected reactivity.

KW - N-HETEROCYCLIC CARBENES

KW - C BOND-CLEAVAGE

KW - VITRO ANTITUMOR-ACTIVITY

KW - IONIC LIQUIDS

KW - ENZOIN CONDENSATION

KW - EFFICIENT

KW - CATALYSIS

KW - ALDEHYDES

KW - DESIGN

KW - TRANSFORMATIONS

U2 - 10.1021/acs.joc.7b00807

DO - 10.1021/acs.joc.7b00807

M3 - Article

C2 - 28561577

SN - 0022-3263

VL - 82

SP - 6232

EP - 6241

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 12

ER -

Developments in the Reactivity of 2-Methylimidazolium Salts

Abstract

Keywords

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