Palladium-Catalyzed Decarboxylative Coupling of Alkynyl Carboxylic Acids with Aryl Tosylates

Ju Hyeon Lee, Gabriel Charles Edwin Raja, Subeen Yu, Junseong Lee, Kwang Ho Song, Sunwoo Lee

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Decarboxylative coupling reactions of alkynyl carboxylic acids with aryl tosylates were developed in the presence of a palladium catalyst. Among the commercially available phosphine ligands, only 1-dicyclohexylphosphino-2-(di-tert-butylphosphino-ethyl)ferrocene (CyPF-tBu) showed good reactivity. The reaction took place smoothly and gave the decarboxylative coupled products in moderate to good yields. This demonstrates the excellent functional group tolerance toward alkyl, alkoxy, fluoro, thiophenyl, ester, and ketone groups. In addition, alkyl-substituted propiolic acids, such as octynoic and hexynoic acids, were coupled with phenyl tosylate to provide the desired products. We found that the electronic properties of the substituents on the phenyl ring in arylpropiolic acids are an important factor. The order of reactivity was found to be aryl iodide > aryl bromide > aryl tosylate > aryl chloride. However, aryl chloride-bearing electron-withdrawing groups showed higher reactivity than those bearing aryl tosylates.

Original languageEnglish
Pages (from-to)6259-6269
Number of pages11
JournalACS Omega
Volume2
Issue number9
DOIs
Publication statusPublished - 2017 Jan 1

Fingerprint

Bearings (structural)
phosphine
Palladium
Carboxylic Acids
Carboxylic acids
Chlorides
Acids
Iodides
Ketones
Bromides
Electronic properties
Functional groups
Esters
Ligands
Catalysts
Electrons

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Palladium-Catalyzed Decarboxylative Coupling of Alkynyl Carboxylic Acids with Aryl Tosylates. / Lee, Ju Hyeon; Raja, Gabriel Charles Edwin; Yu, Subeen; Lee, Junseong; Song, Kwang Ho; Lee, Sunwoo.

In: ACS Omega, Vol. 2, No. 9, 01.01.2017, p. 6259-6269.

Research output: Contribution to journalArticle

Lee, Ju Hyeon ; Raja, Gabriel Charles Edwin ; Yu, Subeen ; Lee, Junseong ; Song, Kwang Ho ; Lee, Sunwoo. / Palladium-Catalyzed Decarboxylative Coupling of Alkynyl Carboxylic Acids with Aryl Tosylates. In: ACS Omega. 2017 ; Vol. 2, No. 9. pp. 6259-6269.
@article{1a02287eff074841a6238b3ab4b757e4,
title = "Palladium-Catalyzed Decarboxylative Coupling of Alkynyl Carboxylic Acids with Aryl Tosylates",
abstract = "Decarboxylative coupling reactions of alkynyl carboxylic acids with aryl tosylates were developed in the presence of a palladium catalyst. Among the commercially available phosphine ligands, only 1-dicyclohexylphosphino-2-(di-tert-butylphosphino-ethyl)ferrocene (CyPF-tBu) showed good reactivity. The reaction took place smoothly and gave the decarboxylative coupled products in moderate to good yields. This demonstrates the excellent functional group tolerance toward alkyl, alkoxy, fluoro, thiophenyl, ester, and ketone groups. In addition, alkyl-substituted propiolic acids, such as octynoic and hexynoic acids, were coupled with phenyl tosylate to provide the desired products. We found that the electronic properties of the substituents on the phenyl ring in arylpropiolic acids are an important factor. The order of reactivity was found to be aryl iodide > aryl bromide > aryl tosylate > aryl chloride. However, aryl chloride-bearing electron-withdrawing groups showed higher reactivity than those bearing aryl tosylates.",
author = "Lee, {Ju Hyeon} and Raja, {Gabriel Charles Edwin} and Subeen Yu and Junseong Lee and Song, {Kwang Ho} and Sunwoo Lee",
year = "2017",
month = "1",
day = "1",
doi = "10.1021/acsomega.7b01165",
language = "English",
volume = "2",
pages = "6259--6269",
journal = "ACS Omega",
issn = "2470-1343",
publisher = "American Chemical Society",
number = "9",

}

TY - JOUR

T1 - Palladium-Catalyzed Decarboxylative Coupling of Alkynyl Carboxylic Acids with Aryl Tosylates

AU - Lee, Ju Hyeon

AU - Raja, Gabriel Charles Edwin

AU - Yu, Subeen

AU - Lee, Junseong

AU - Song, Kwang Ho

AU - Lee, Sunwoo

PY - 2017/1/1

Y1 - 2017/1/1

N2 - Decarboxylative coupling reactions of alkynyl carboxylic acids with aryl tosylates were developed in the presence of a palladium catalyst. Among the commercially available phosphine ligands, only 1-dicyclohexylphosphino-2-(di-tert-butylphosphino-ethyl)ferrocene (CyPF-tBu) showed good reactivity. The reaction took place smoothly and gave the decarboxylative coupled products in moderate to good yields. This demonstrates the excellent functional group tolerance toward alkyl, alkoxy, fluoro, thiophenyl, ester, and ketone groups. In addition, alkyl-substituted propiolic acids, such as octynoic and hexynoic acids, were coupled with phenyl tosylate to provide the desired products. We found that the electronic properties of the substituents on the phenyl ring in arylpropiolic acids are an important factor. The order of reactivity was found to be aryl iodide > aryl bromide > aryl tosylate > aryl chloride. However, aryl chloride-bearing electron-withdrawing groups showed higher reactivity than those bearing aryl tosylates.

AB - Decarboxylative coupling reactions of alkynyl carboxylic acids with aryl tosylates were developed in the presence of a palladium catalyst. Among the commercially available phosphine ligands, only 1-dicyclohexylphosphino-2-(di-tert-butylphosphino-ethyl)ferrocene (CyPF-tBu) showed good reactivity. The reaction took place smoothly and gave the decarboxylative coupled products in moderate to good yields. This demonstrates the excellent functional group tolerance toward alkyl, alkoxy, fluoro, thiophenyl, ester, and ketone groups. In addition, alkyl-substituted propiolic acids, such as octynoic and hexynoic acids, were coupled with phenyl tosylate to provide the desired products. We found that the electronic properties of the substituents on the phenyl ring in arylpropiolic acids are an important factor. The order of reactivity was found to be aryl iodide > aryl bromide > aryl tosylate > aryl chloride. However, aryl chloride-bearing electron-withdrawing groups showed higher reactivity than those bearing aryl tosylates.

UR - http://www.scopus.com/inward/record.url?scp=85042188377&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85042188377&partnerID=8YFLogxK

U2 - 10.1021/acsomega.7b01165

DO - 10.1021/acsomega.7b01165

M3 - Article

AN - SCOPUS:85042188377

VL - 2

SP - 6259

EP - 6269

JO - ACS Omega

JF - ACS Omega

SN - 2470-1343

IS - 9

ER -