Palladium-Catalyzed Direct Dehydrogenative Annulation of Ferrocenecarboxamides with Alkynes in Air

Xie, Wucheng; Li, Bin; Xu, Shansheng; Song, Haibin; Wang, Baiquan

doi:10.1021/om5002606

Cited by 37 publications

(9 citation statements)

References 88 publications

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“…Wang et al developed a synthesis of racemic ferrocene[1,2- c ]pyridine-3(4 H )-ones 67 via Pd/Cu-catalyzed direct dehydrogenative annulations of ferrocene-carboxamides 66 with internal alkynes under air (Scheme ). The reaction also proceeds via C–H activation by amide precoordinated Pd species. The role of the Cu salt is reoxidation in the presence of air oxygen.…”

Section: Palladium-catalyzed Reactionsmentioning

confidence: 75%

Alkenylation of Arenes and Heteroarenes with Alkynes

et al. 2016

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This review is focused on the analysis of current data on new methods of alkenylation of arenes and heteroarenes with alkynes by transition metal catalyzed reactions, Bronsted/Lewis acid promoted transformations, and others. The synthetic potential, scope, limitations, and mechanistic problems of the alkenylation reactions are discussed. The insertion of an alkenyl group into aromatic and heteroaromatic rings by inter- or intramolecular ways provides a synthetic route to derivatives of styrene, stilbene, chalcone, cinnamic acid, various fused carbo- and heterocycles, etc.

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Section: Palladium-catalyzed Reactionsmentioning

confidence: 75%

Alkenylation of Arenes and Heteroarenes with Alkynes

et al. 2016

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“…Some complementary approaches to pyridone-fused ferrocenes are based on tran- In 2014, Wang and co-workers reported the efficient synthesis of racemic ferrocene[1,2,c]pyridine-3(4H)-ones through Pd-catalyzed dehydrogenative annulation of ferrocenecarboxamides with internal alkynes using stoichiometric copper acetate and air as the terminal oxidants (Scheme 16A). [44] Afterwards, You and co-workers described the synthesis of N-unprotected pyridinones through Rh(III)-catalyzed annulation of N-methoxy ferrocenecarboxamides with internal alkynes using a directing group as an internal oxidant (Scheme 16B). [45] In the case of unsymmetrical alkynes, this coupling reaction was found to proceed with complete regioselectivity.…”

Section: Synthesis and Applications Of Pyridinone-fused Ferrocene Der...mentioning

confidence: 99%

Synthesis and Applications of Ferrocene‐Fused Nitrogen Heterocycles

2021

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The marriage of heterocyclic compounds with ferrocene has proven to be an extremely fruitful field of research. In fact, in the last years, several ferrocene-embedded heterocyclic compounds have been reported. In some cases, the synergistic combination of the properties of the heterocyclic and metal-lacyclic motifs provides to the fused systems interesting applications. This Review summarizes the major advances in the synthesis of ferrocene-fused nitrogen heterocyclic compounds and their applications, particularly in asymmetric catalysis.

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“…In 2014, Wang discovered a Pd-catalyzed annulation reaction of ferrocenecarboxamides with internal alkynes . The lack of a requirement for ligands in this process presents a formidable challenge for developing a chiral version.…”

Section: Enantioselective Synthesis Of Planar Chiral Ferrocenes Via I...mentioning

confidence: 99%

Synthesis of Planar Chiral Ferrocenes via Transition-Metal-Catalyzed Direct C–H Bond Functionalization

et al. 2017

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Ferrocenes are of great interest in the fields of materials science, organic synthesis, and biomedical research. Of particular significance is the fact that ferrocenes bearing planar chirality have been demonstrated to be highly efficient ligands or catalysts in asymmetric catalysis, some of which have been employed in the industrial synthesis of pharmaceuticals and agrochemicals. So far, the main methods for the synthesis of planar chiral ferrocenes involve diastereoselective directed ortho-metalation (DoM), enantioselective DoM, and chiral resolution. Despite the fact that these approaches are well developed and widely applied, the use of chiral auxiliaries or external stoichiometric chiral bases is required in most cases. Additionally, the practicality of these processes is hampered by the requirement of sensitive organometallic reagents, the poor compatibility with functional groups, and the low atom economy in some cases. Therefore, the development of highly efficient strategies to introduce planar chirality on the backbone of ferrocene that do not possess these limitations is highly desirable. Meanwhile, transition-metal-catalyzed asymmetric C-H bond functionalization reactions have attracted much attention over the past few years owing to their emerging potential for providing a straightforward approach for the preparation of chiral molecules. In addition to the majority of the work focusing on the installation of central chirality, methods for the catalytic asymmetric synthesis of planar chiral compounds via C-H bond functionalization have also been explored. In this Account, we summarize our recent efforts aimed at the development of novel methods to synthesize planar chiral compounds via asymmetric C-H bond functionalization and also highlight related achievements by other groups. First, we briefly introduce the precedent examples of diastereoselective and enantioselective synthesis of planar chiral ferrocenes. Subsequently, asymmetric syntheses of structurally diverse planar chiral ferrocenes via Pd [Pd(II), Pd(0)]-, Ir-, Rh-, Au-, and Pt-catalyzed C-H bond functionalization are described. These methods have impressive advantages over traditional approaches for the synthesis of functionalized planar chiral ferrocenes in terms of both step- and atom-economies. Notably, the products of these processes are easily transformed into a variety of new catalysts or ligands, which have been demonstrated to promote efficient asymmetric reactions. Moreover, DFT calculations have been conducted to explore the origin of the excellent enantioselectivity of Pd-catalyzed enantioselective C-H bond functionalization reactions. Progress made in the area of asymmetric C-H bond functionalization provides an effective platform for the design and synthesis of planar chiral ferrocenes.

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Palladium-Catalyzed Direct Dehydrogenative Annulation of Ferrocenecarboxamides with Alkynes in Air

Abstract: A novel method to synthesize racemic ferrocene[1,2-c]pyridine-3(4H)-ones via Pd-catalyzed direct dehydrogenative annulations of ferrocenecarboxamides with internal alkynes in air has been developed. Both alkyl and aryl ferrocenecarboxamides can be applied as effective substrates.

Cited by 37 publications

References 88 publications

Alkenylation of Arenes and Heteroarenes with Alkynes

Alkenylation of Arenes and Heteroarenes with Alkynes

Synthesis and Applications of Ferrocene‐Fused Nitrogen Heterocycles

Synthesis of Planar Chiral Ferrocenes via Transition-Metal-Catalyzed Direct C–H Bond Functionalization

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