Synthesis of Difluorinated Enynes through Sonogashira-Type Coupling

Fujino, Takumi; Hinoue, Teruo; Usuki, Yoshinosuke; Satoh, Toshifumi

doi:10.1021/acs.orglett.6b02919

Cited by 31 publications

(10 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The cross-coupling reactions of 2,2-difluoroethenyl tosylate appear to be promising approaches toward such 1,1-difluoro-1-alkene compounds because this tosylate is readily attained from 2,2,2-trifluoroethanol which has been widely employed as a solvent in organic synthesis. Skrydstrup and Satoh have independently reported a straightforward method for the synthesis of 1,1-difluoro-1-alkene compounds via Suzuki–Miyaura and Sonogashira-type couplings with 2,2-difluoroethenyl tosylate . Transition metal-catalyzed direct functionalization of substrates by C–H bond activation would eliminate the need for prefunctionalization of coupling partners and apparently, the direct functionalization involving C–H bond activation would provide simple and practical pathways for making functionalized molecules.…”

Section: Introductionmentioning

confidence: 99%

Cp*Rh(III)-Catalyzed C–H Bond Difluorovinylation of Indoles with α,α-Difluorovinyl Tosylate

Yang

Wang

et al. 2019

J. Org. Chem.

View full text Add to dashboard Cite

Unprecedented Rh(III)-catalyzed C–H bond difluorovinylation of indoles has been successfully developed, and this method provided an example of direct difluorovinylation reaction through C–H bond activation which was rarely reported. In this context, N-ethoxycarbamoyl served as the directing group and 2,2-difluorovinyl tosylates were used for the construction of difluorovinyl-substituted indoles. This method provided a practical strategy for difluorovinylation of indoles with moderate to good yields and is characterized by the broad synthetic utility, mild conditions, and high efficiency.

show abstract

Section: Introductionmentioning

confidence: 99%

Cp*Rh(III)-Catalyzed C–H Bond Difluorovinylation of Indoles with α,α-Difluorovinyl Tosylate

Yang

Wang

et al. 2019

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…The Pd-catalyzed coupling of 2,2-difluorovinyl tosylate with various aliphatic and aromatic terminal alkynes was reported by the Satoh group in 2016 (Scheme 9). 13 There was only one reported example of the coupling of 2,2-difluorovinyl tosylate with phenylpropynoic acid using Pd(PPh 3 ) 4 (5 mol%) with 1.5 equiv of CuI at room temperature to give 1,1-difluoro-4-phenylbut-1-en-3-yne in 74% yield.…”

Section: Pd-catalyzed Coupling Of Pseudohalidesmentioning

confidence: 99%

Recent Advances in Decarboxylative Reactions of Alkynoic Acids

Idris

Lee

2020

Synthesis

View full text Add to dashboard Cite

Alkynoic acids have been widely employed as alkyne and alkene sources in decarboxylative reactions. Alkynoic acid coupling leads to the formation of direct coupling products and cyclized products through sequential reactions. Moreover, homocoupling and multicomponent reactions have been developed. The decarboxylative addition of alkynoic acids generates the corresponding alkene products. A number of synthetic methods are utilized for the preparation of arylpropynoic acids including the Sonogashira coupling and the carboxylation of terminal alkynes. Recently, the use of decarboxylative halogenations has also been reported. This review covers decarboxylative reactions of alkynoic acids reported between 2013 and 2019; further, it is divided into several sections according to the type of reaction.1 Introduction2 Direct Coupling3 Sequential Reactions4 Homocoupling5 Multicomponent Reactions6 Addition7 Halogenations8 Synthesis of Alkynoic Acids9 Conclusion

show abstract

“…Very recently, Satoh’s group reported the Sonogashira-type coupling of 2,2-difluorophenyl tosylate with phenylpropiolic acid to obtain difluorinated enynes. 15 However, their method is limited to 2,2-difluoroethynyl tosylate and the coupling with aryl tosylates was not successful. Moreover, aryl tosylates are much less reactive than vinyl tosylates.…”

Section: Introductionmentioning

confidence: 99%

“…Although considerable related results have been achieved since our first report concerning decarboxylative coupling reactions, this type of reaction with aryl tosylates has not been previously reported. Very recently, Satoh’s group reported the Sonogashira-type coupling of 2,2-difluorophenyl tosylate with phenylpropiolic acid to obtain difluorinated enynes . However, their method is limited to 2,2-difluoroethynyl tosylate and the coupling with aryl tosylates was not successful.…”

Section: Introductionmentioning

confidence: 99%

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

Lee

Raja

et al. 2017

ACS Omega

View full text Add to dashboard Cite

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- t Bu) 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.

show abstract

Synthesis of Difluorinated Enynes through Sonogashira-Type Coupling

Cited by 31 publications

References 66 publications

Cp*Rh(III)-Catalyzed C–H Bond Difluorovinylation of Indoles with α,α-Difluorovinyl Tosylate

Cp*Rh(III)-Catalyzed C–H Bond Difluorovinylation of Indoles with α,α-Difluorovinyl Tosylate

Recent Advances in Decarboxylative Reactions of Alkynoic Acids

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

Contact Info

Product

Resources

About