Palladium-catalyzed carbonylative coupling of α-chloroketones with hydrazines: a simple route to pyrazolone derivatives

Capua, Martina; Granito, Catia; Perrone, Serena; Salomone, Antonio; Troisi, Luigino

doi:10.1016/j.tetlet.2016.06.072

Cited by 18 publications

(15 citation statements)

References 34 publications

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“…The 1,3‐bifunctional β ‐oxo acylpalladium complex 2 (Scheme ) has shown to be very reactive not only towards 1,3‐bidentate nucleophiles (urea and guanidine derivatives), leading to six‐membered rings, but also towards 1,2‐bidentate nucleophiles such as hydrazines, to afford five‐membered cycles. Particularly, when aliphatic or aromatic chloromethyl‐ketones were carbonylated in the presence of aromatic or aliphatic hydrazines, the one‐pot reaction afforded two isomeric five‐membered N ‐heterocycles such as pyrazol‐5‐one 7 and pyrazole‐3‐one derivatives 8 (Scheme ) …”

Section: Synthesis Of N‐heterocyclesmentioning

confidence: 99%

“…Reaction regioselectivity is strongly influenced by the stereoelectronic nature of the substrates and it is significantly improved towards the pyrazol‐5‐one derivative with the use of sterically demanding starting materials (i.e. chloropinacolone, tert ‐butylhydrazine) …”

Section: Synthesis Of N‐heterocyclesmentioning

confidence: 99%

“…The formation of the two N ‐heterocyclic isomers 7 and 8 could be explained through two possible carbonylation processes involving both the starting α ‐chloroketone and the α ‐chlorohydrazone derived from the preliminary condensation between the two starting reagents ( α ‐chloroketone and hydrazine) …”

Section: Synthesis Of N‐heterocyclesmentioning

confidence: 99%

“…Particularly, when aliphatic or aromatic chloromethyl-ketones were carbonylated in the presence of aromatic or aliphatic hydrazines, the one-pot reaction afforded two isomeric fivemembered N-heterocycles such as pyrazol-5-one 7 and pyrazole-3-one derivatives 8 (Scheme 5). [21] Scheme 5. Carbonylative synthesis of pyrazolone derivatives from α-chloroketones and hydrazine derivatives.…”

Section: Introductionmentioning

confidence: 99%

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Heterocycle Synthesis through Pd‐Catalyzed Carbonylative Coupling

2019

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Heterocyclic chemistry is one of the most important and attractive areas of organic chemistry. It involves the preparation of compounds endowed with very high structural diversity and plays a central role in a multitude of highly developed areas: fine chemicals, drugs, flavors, dyes, engineered materials, and many other kinds of products contain at least one heterocyclic ring in their molecular structure. Therefore, the discovery of new methods for heterocycle synthesis is a significant objective of modern organic chemists, especially if prepared in environmentally benign and synthetically efficient ways. In this context, this minireview focuses on the synergy of two green strategies, namely multicomponent reactions and palladium‐catalyzed carbonylations, for the construction of a wide variety of heterocyclic systems. These processes are of considerable interest because they combine synthetic efficiency with respect for the environment.

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Section: Synthesis Of N‐heterocyclesmentioning

confidence: 99%

Section: Synthesis Of N‐heterocyclesmentioning

confidence: 99%

Section: Synthesis Of N‐heterocyclesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Heterocycle Synthesis through Pd‐Catalyzed Carbonylative Coupling

2019

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“…In recent years, transition metal‐catalyzed annulation reactions were ranked among the most powerful and simple methods for the synthesis of pyrazoles and their derivatives . Numerous transition metals such as Cu, Rh, Ru, Pd, Pt and Au have been widely applied to catalyze the annulation reactions for synthesizing pyrazoles and their derivatives . Among the various transition metal catalysts, gold has gained much attention and brought a new “gold rush” for the discovery of novel organic transformations in the past decade, because of the specific carbophilic π‐acidic and catalytic activities of gold‐complexes which are stable to air and moisture …”

Section: Introductionmentioning

confidence: 99%

Mechanistic study on gold(I)‐catalyzed crosscoupling of diazo compounds: A DFT study

Tian

Liang

2017

Int J of Quantum Chemistry

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The reaction mechanisms of the gold(I)‐catalyzed cross‐coupling reaction of aryldiazoacetate R1 with vinyldiazoacetate R2 leading to N‐substituted pyrazoles have been theoretically investigated using density functional theory calculations. Two possible reaction mechanisms were examined and discussed. The preferred reaction mechanism (mechanism A) can be characterized by five steps: the formation of the gold carbenoid A2 via the attack of catalyst to R1 (step I), nucleophilic addition of another reactant R2 to generate intermediate A3 (step II), intramolecular cyclization of A3 to form intermediate A4 (step III), hydrogen migration to give intermediate A5 (step IV), and catalyst elimination affording the final product P1 (step V). Step IV is found to be the rate‐determining step with an overall free energy barrier of 28.3 kcal/mol. Our calculated results are in good agreement with the experimental observations. The present study may provide a useful guide for understanding these kinds of gold(I)‐catalyzed cross‐coupling reactions of diazo compounds.

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Pd‐catalyzed Three‐component Cross‐coupling of Arylhydrazides with Arylboronic Acids and TFBen: Facile Access to Diaryl Ketones via Denitrogenative Carbonylation

Zhang,

Ai,

Wang

et al. 2023

Asian J Org Chem

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Carbonylation with CO surrogates is one of the most common methods for introduction of carbonyl groups in ketone synthesis. However, arylhydrazides have not been used as an aryl source in this denitrogenative method even though they are cheap and accessible. Here, we report development of palladium catalysis for the three‐component reactions of arylboronic acids, CO‐surrogates (benzene‐1,3,5‐triyl triformate), and arylhydrazides under oxygen conditions to produce diaryl ketones. (Hetero)arylhydrazides, as well as (hetero)arylboronic acids are suitable reaction partners, and good functional group compatibility was achieved. This method could be used for streamlined synthesis of diaryl ketones, ketoprofen and fenofibrate.

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Palladium-catalyzed carbonylative coupling of α-chloroketones with hydrazines: a simple route to pyrazolone derivatives

Cited by 18 publications

References 34 publications

Heterocycle Synthesis through Pd‐Catalyzed Carbonylative Coupling

Heterocycle Synthesis through Pd‐Catalyzed Carbonylative Coupling

Mechanistic study on gold(I)‐catalyzed crosscoupling of diazo compounds: A DFT study

Pd‐catalyzed Three‐component Cross‐coupling of Arylhydrazides with Arylboronic Acids and TFBen: Facile Access to Diaryl Ketones via Denitrogenative Carbonylation

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