Carboxylative coupling reaction of five-membered (chloromethyl)heteroarenes with allyltributylstannane catalyzed by palladium nanoparticles

doi:10.1016/j.tetlet.2015.10.061

Tetrahedron Letters

Volume 56, Issue 48, 2 December 2015, Pages 6747-6750

https://doi.org/10.1016/j.tetlet.2015.10.061 Get rights and content

Abstract

The palladium-catalyzed three-component coupling reaction of five-membered (chloromethyl)heteroarenes, allyltributylstannane, and carbon dioxide (carboxylative Stille coupling reaction) was successfully conducted to produce β,γ-unsaturated esters in satisfactory to good yields. The carboxylative Stille coupling reaction occurred smoothly under mild conditions in the presence of palladium nanoparticles through the formation of π-allylpalladium chloride intermediates.

Graphical abstract

Palladium-catalyzed chemical fixation of CO₂ is successfully achieved using the π-allyl group related to heterocycles as a carbon-based ligand. The PdNPs generated in situ played a key role for the success in the carboxylative Stille coupling reaction.

Introduction

Construction of a new C–C bond with carbon dioxide (CO₂) is one of the important methods of chemical fixation of CO₂.¹ Although Grignard reagents and organic lithium reagents can directly react with CO₂ to generate new C–C bonds, they cannot be widely utilized because of their poor functional group tolerance. Therefore, the development of new methods for chemical fixation of CO₂ involving new carbon–carbon bond formation is of utmost importance. Transition metal-catalyzed activation and conversion of CO₂ into valuable chemicals have recently emerged as extremely powerful tools because of their high chemoselectivity, good functional group tolerance, and mild reaction conditions.² In transition metal catalysis, the use of appropriate ligands is necessary for the success of chemical fixation of CO₂. Over the past four decades, three main kind of ligands, namely, P-containing ligands,3, 4, 5, 6 N-containing ligands,⁷ and N-heterocyclic carbene ligands,⁸ have been successfully used in the transition metal-catalyzed activation and conversion of CO₂.We have recently reported that π-benzyl can be used as a carbon-based ligand for palladium-catalyzed chemical fixation of CO₂, namely, the palladium-catalyzed carboxylative Stille coupling reaction of benzyl chlorides with allyltributylstannane.⁹ Recently, we found that five-membered 2-(chloromethyl)heteroarenes can also react with palladium(0) to form π-allylpalladium(II) chloride intermediate.¹⁰ Based on this discovery, we hypothesized that the π-allyl involving heterocycles may also be used as a carbon-based ligand for palladium-catalyzed chemical fixation of CO₂. As expected, the carboxylative Stille coupling reaction of 2-(chloromethyl)heteroarenes with allyltributylstannane occurred in the presence of palladium nanoparticles (PdNPs). The results are reported in the current work.

Section snippets

Result and discussion

In our initial studies, the carboxylative coupling reaction of 2-(chloromethyl)thiophene (1a) with allyltributylstannane was chosen as a model to optimize the reaction conditions. The results are shown in Table 1. When the reaction of 1a with allyltributylstannane was carried out under similar conditions as employed in the Stille-type allylation of 1a with allyltributylstannane,¹⁰ an allylated product 2a′ was obtained in 52% yield even though the reaction was conducted under 2.0 MPa of CO₂

Conclusion

In summary, we have developed a novel and efficient method for the palladium-catalyzed chemical fixation of CO₂ using the π-allyl group related to heterocycles as a carbon-based ligand. The PdNPs generated in situ played a key role for the success in the carboxylative coupling of five-membered 2- or 3-(chloromethyl)heteroarenes with allyltributylstannane. Further studies focusing on the telomerization of 1,3-butadiene with CO₂ using π-allyl carbon-based ligands in the presence of PdNPs as the

Acknowledgments

We are grateful to the National Natural Science Foundation of China (Nos. 21173032 and 21373041) for their financial support. The authors acknowledge the Deanship of Scientific Research at King Saud University for the Research Grant, RGP-VPP-026.

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Carboxylative coupling reaction of five-membered (chloromethyl)heteroarenes with allyltributylstannane catalyzed by palladium nanoparticles

Abstract

Graphical abstract

Introduction

Section snippets

Result and discussion

Conclusion

Acknowledgments

Chem. Rev.

Angew. Chem., Int. Ed.

Angew. Chem., Int. Ed.

Angew. Chem., Int. Ed.

Chem. Commun.

J. Chem. Soc., Chem. Commun.

J. Org. Chem.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Org. Lett.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Chem. Soc., Chem. Commun.

Chem. Lett.

Chem. Lett.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.