Synthesis of β-enamino acid and heteroaryl acetic acid derivatives by Pd-catalyzed carbonylation of α-chloroimines and 2-chloromethyl aza-heterocycles

Perrone, Serena; Capua, Martina; Cannazza, Giuseppe; Salomone, Antonio; Troisi, Luigino

doi:10.1016/j.tetlet.2016.02.035

Cited by 13 publications

(6 citation statements)

References 27 publications

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“…We have shown how its use can be extended by transforming them into α‐chloromethyl oxime ethers, which are suitable substrates for easy Pd(0) catalyzed cross‐coupling and carbonylative cross‐coupling reactions with boronic acids, alcohols and amine . More recently α‐chloromethylimines and 2‐chloromethylaza‐heterocycles have also been used successfully in this type of Pd(0) catalyzed transformations . With this background (Scheme ) we wonder if the phenyl amino group present in the ((arylimino)methyl)palladium(II) chloride complex resulting from the oxidative addition of a Pd(0) complex to an α‐chloromethylimine would undergo ortho palladation and subsequent coupling to provide a new and direct route to the indole ring.…”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed C–C Ring Closure in α‐Chloromethylimines: Synthesis of 1H‐Indoles

et al. 2018

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The C‐C ring closure of α‐chloromethyl alkyl or aryl N‐aryl imines catalyzed with 1 to 10 % Pd(OAc)2/P(p‐tolyl)3 afford efficiently 2‐aryl‐ and 2‐alkyl‐1H‐indoles. The heterocyclization reaction involves the initial formation of [2‐(arylimino)ethyl]palladium(II) chloride complexes with subsequent C‐H activation of the aromatic amine ring. Readily or commercially available α‐chloromethyl‐aryl or ‐alkyl ketones are used as the precursors. Functionalized indoles at the benzene ring are obtained when the imines are derived from substituted anilines.

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Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed C–C Ring Closure in α‐Chloromethylimines: Synthesis of 1H‐Indoles

et al. 2018

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“…On the other hand, there are some critical drawbacks, related to the use of gaseous H 2 such as the very broad flammability range of hydrogen gas, [32] the need to use suitable reactors when the process occurs at high pressure and the huge energy demand and large emission of greenhouse gases to produce molecular hydrogen by natural gas reforming. [33] Based on their research on Pd-catalyzed reactions and sustainable synthetic processes in DESs, [34][35][36][37][38][39][40][41][42][43] Messa et al, very recently, described a safe, scalable and sustainable HY reaction of a variety of functional groups. The reactions, enabled by in situ generation of hydrogen from Al powder and small amount of basic water, were catalyzed by the cheap Pd/C catalyst.…”

Section: Reductions In Deep Eutectic Solventsmentioning

confidence: 99%

“…Based on their research on Pd‐catalyzed reactions and sustainable synthetic processes in DESs, [34–43] Messa et al., very recently, described a safe, scalable and sustainable HY reaction of a variety of functional groups. The reactions, enabled by in situ generation of hydrogen from Al powder and small amount of basic water, were catalyzed by the cheap Pd/C catalyst.…”

Section: Reductions In Deep Eutectic Solventsmentioning

confidence: 99%

Towards Green Reductions in Bio‐Derived Solvents

2023

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The hydrogenation processes, and all the reactions that formally add two hydrogen atoms to an unsaturated bond, are among the most used transformations in the manufacture of bulk and fine chemicals. Although their potential as powerful tool for the sustainable synthesis of organic compounds, hydrogenations, and more generally the reductions, have been typically carried out in volatile organic solvents deriving from petroleum; indeed, all studies and fascinating advances related to the catalysts’ activity or the reducing agents’ reactivity have been limited to such volatile and often toxic reaction media. In this review, recent advances in the reducing methodologies with an improved degree of sustainability have been described. In particular, a series of examples have been reported to highlight the chance to reduce an organic compound by using a benign solvent deriving from renewable sources, without waiving to the process efficiency and selectivity. Some important key points of green chemistry, such as the easiness of catalyst recovery or the simplicity of product isolation, have been considered in the choice of the described studies.

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“…Such sustainable reductive methodologies w also used to prepare reduced six-membered N-heterocycles. As a part of our ong interest in metal-catalyzed reactions [57][58][59][60][61] and sustainable synthetic methodolo [14,40,62,63], a Pd/C-catalyzed reductive process, involving in situ generation of from Al powder and basic water, was recently developed in the bio-based ChC eutectic mixture for the hydrogenation of a variety of organic compounds and for de-aromatization of heteroaromatic rings such as quinoline (Scheme 23) Particularly, the quinoline heterocycle could be smoothly reduced in a good yiel Reductive strategies can be employed for the preparation of N-heterocycles. Hydrogenation reactions, and more generally the reductions, providing a direct route for the formation of C-H, N-H, and O-H bonds, are among the most used transformations in the manufacture of pharmaceuticals, bulk, and fine chemicals [53][54][55].…”

Section: For Peer Review 12 Omentioning

confidence: 99%

N-, O- and S-Heterocycles Synthesis in Deep Eutectic Solvents

et al. 2023

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The synthesis of heterocycles is a fundamental area of organic chemistry that offers enormous potential for the discovery of new products with important applications in our daily life such as pharmaceuticals, agrochemicals, flavors, dyes, and, more generally, engineered materials with innovative properties. As heterocyclic compounds find application across multiple industries and are prepared in very large quantities, the development of sustainable approaches for their synthesis has become a crucial objective for contemporary green chemistry committed to reducing the environmental impact of chemical processes. In this context, the present review focuses on the recent methodologies aimed at preparing N-, O- and S-heterocyclic compounds in Deep Eutectic Solvents, a new class of ionic solvents that are non-volatile, non-toxic, easy to prepare, easy to recycle, and can be obtained from renewable sources. Emphasis has been placed on those processes that prioritize the recycling of catalyst and solvent, as they offer the dual benefit of promoting synthetic efficiency while demonstrating environmental responsibility.

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Synthesis of β-enamino acid and heteroaryl acetic acid derivatives by Pd-catalyzed carbonylation of α-chloroimines and 2-chloromethyl aza-heterocycles

Cited by 13 publications

References 27 publications

Palladium‐Catalyzed C–C Ring Closure in α‐Chloromethylimines: Synthesis of 1H‐Indoles

Palladium‐Catalyzed C–C Ring Closure in α‐Chloromethylimines: Synthesis of 1H‐Indoles

Towards Green Reductions in Bio‐Derived Solvents

N-, O- and S-Heterocycles Synthesis in Deep Eutectic Solvents

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