N-Propargylation and Copper(I)-Catalyzed Azide-Alkyne Cycloaddition as a Convenient Strategy for Directed Post-Synthetic Modification of 4-Oxo-1,4-Dihydrocinnoline Derivatives

Mikhaylov, Vladimir N.; Pavlov, A. O.; Ogorodnov, Yaroslav V.; Spiridonova, Dar’ya V.; Sorokoumov, V. N.; Балова, Ирина А.

doi:10.1007/s10593-020-02750-0

Cited by 9 publications

(4 citation statements)

References 47 publications

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“…These facts can point at the establishment of the dynamic equilibrium between the (IMes)CuY and [(IMes) 2 Cu] + [CuY 2 ]forms, depending on the nucleophilicity of anion Y and the solvent nature. Such equilibrium has been observed for the (NHC)Ag(I) [136], (NHC)Cu(I) [137,203], and (NHC)Au(I) [98] complexes.…”

Section: Reactions With the Formation Of Bimetallic Adducts Retaining The Nhc-m с Bondsupporting

confidence: 56%

“…The formation of biscarbene silver(I) and copper(I) complexes can be explained by the equilibrium shown in Scheme 26, which has been observed in a solution of the N-heterocyclic complexes of silver(I) [136] and copper(I) [137]. The Lewis acid has possibly promoted the equilibrium shift towards the formation of the homoleptic complex due to the complex formation with the halide anion, which has resulted in precipitation of the insoluble silver(I) salt.…”

Section: Transformation Of Heteroleptic N-heterocyclic Carbene Complexes (Nhc)m C X Into Cationic Homoleptic Complexes [(Nhc) 2 M C ] + Umentioning

confidence: 91%

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Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Mikhaylov

Балова

2021

Russ J Gen Chem

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The carbene transfer from N-heterocyclic carbene complexes of Group 11 metals (NHC-M C ) (especially silver and copper) to other metals is considered a convenient and universal, sometimes having no alternative, method for the synthesis of a wide range of important N-heterocyclic carbene complexes of transition metals. As the number of successful examples of transmetalation with the formation of the target product has increased, the data were accumulated on alternative or unexpected results of the interaction of NHC-M C complexes with compounds of other metals. This review considers the examples of NHC-M C reactions with compounds of other metals which proceed with a change in the metals oxidation state, conversion of (NHC)M C X into cationic homoleptic [(NHC) 2 M C ] + forms, transmetalation retaining the other metal in the coordination sphere of the product, or formation of heterometallic adducts preserving the M C -C carbene bond, rather than these occurring according to the standard reaction pathway. Unusual "reverse" carbene transfer reactions have been considered separately. The review material reveals a promising new synthetic potential of NHC-M C in the reactions with other metals and discusses the possible mechanisms and driving forces of such transformations. The most important aspects of the application of the obtained products, primarily in various catalytic processes, have been considered as well.

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Section: Reactions With the Formation Of Bimetallic Adducts Retaining The Nhc-m с Bondsupporting

confidence: 56%

Section: Transformation Of Heteroleptic N-heterocyclic Carbene Complexes (Nhc)m C X Into Cationic Homoleptic Complexes [(Nhc) 2 M C ] + Umentioning

confidence: 91%

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Mikhaylov

Балова

2021

Russ J Gen Chem

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“…It was noted that the complexes of the [(IPr)CuX] series (X = Cl, Br, I) did not exhibit catalytic activity. However, [(IMes)CuX] complexes (X = Cl, Br, I) containing a less sterically hindered ligand showed higher activity under the same reaction conditions; this was attributed to the electronic nature of the halides, and the catalytic reactivity increased in the order of Cl − < Br − ≈ I − , (Scheme 60) [45]. N-Propargylated cinnolinones 145a-c reacted with benzyl azide to afford the corresponding triazole derivatives 146a-c via CuAAC in CHCl3.…”

Section: Synthesis Of the Triazole Ringmentioning

confidence: 99%

“…It was noted that the complexes of the [(IPr)CuX] series (X = Cl, Br, I) did not exhibit catalytic activity. However, [(IMes)CuX] complexes (X = Cl, Br, I) containing a less sterically hindered ligand showed higher activity under the same reaction conditions; this was attributed to the electronic nature of the halides, and the catalytic reactivity increased in the order of Cl − < Br − ≈ I − , (Scheme 60) [45]. Filimonov et al [46] reported a one-step, eco-friendly method for synthesizing 1,2,3thiadiazol-4-carbimidamides 149a-r and 1,2,3-triazole-4-carbothioamides 150a-j, during the reactions of 2-cyanothioacetamides 147a-g with various types of azides 148 in water in the presence of alkali (Scheme 61).…”

Section: Synthesis Of the Triazole Ringmentioning

confidence: 99%

Azides in the Synthesis of Various Heterocycles

et al. 2022

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In this review, we focus on some interesting and recent examples of various applications of organic azides such as their intermolecular or intramolecular, under thermal, catalyzed, or noncatalyzed reaction conditions. The aforementioned reactions in the aim to prepare basic five-, six-, organometallic heterocyclic-membered systems and/or their fused analogs. This review article also provides a report on the developed methods describing the synthesis of various heterocycles from organic azides, especially those reported in recent papers (till 2020). At the outset, this review groups the synthetic methods of organic azides into different categories. Secondly, the review deals with the functionality of the azido group in chemical reactions. This is followed by a major section on the following: (1) the synthetic tools of various heterocycles from the corresponding organic azides by one-pot domino reaction; (2) the utility of the chosen catalysts in the chemoselectivity favoring C−H and C-N bonds; (3) one-pot procedures (i.e., Ugi four-component reaction); (4) nucleophilic addition, such as Aza-Michael addition; (5) cycloaddition reactions, such as [3+2] cycloaddition; (6) mixed addition/cyclization/oxygen; and (7) insertion reaction of C-H amination. The review also includes the synthetic procedures of fused heterocycles, such as quinazoline derivatives and organometal heterocycles (i.e., phosphorus-, boron- and aluminum-containing heterocycles). Due to many references that have dealt with the reactions of azides in heterocyclic synthesis (currently more than 32,000), we selected according to generality and timeliness. This is considered a recent review that focuses on selected interesting examples of various heterocycles from the mechanistic aspects of organic azides.

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Transition Metal Complexes of NHC Ligands Functionalized with the Cationic (η⁵‐Cyclopentadienyl)(η⁶‐phenyl)iron(II) Motif

et al. 2022

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Starting from [(η5‐cyclopentadienyl)(η6‐phenyl)iron(II)]imidazole, dicationic imidazolium salts were prepared by N‐alkylation. Reaction of these compounds with basic metal precursors such as mesityl copper(I) or palladium(II) acetate led to mono respectively dicationic transition metal NHC complexes (NHC=N‐heterocyclic carbene). Transmetalation using the copper(I) complexes opened up the access to NHC gold(I) compounds. PEPPSI‐type NHC complexes of palladium(II) and platinum(II) were prepared by offering a neutral pyridine ligand to the transition metal center. A rhodium(I) NHC complex was accessible by deprotonation of the dicationic imidazolium precursor and subsequent treatment with [(COD)Rh(μ2‐Cl)]2 (COD=1,5‐cyclooctadiene). The new NHC complexes were investigated by means of NMR spectroscopy, mass spectrometry as well as single crystal X‐ray structure analysis. Both, the palladium(II) containing PEPPSI‐type and the gold(I) complex, were investigated for their catalytic properties in typical model reactions such as cyclization reactions, Suzuki coupling and cyanation. In addition, a selenium adduct was synthesized in order to study the electronic properties of the underlying ligand backbone. Based on the chemical shift in the 77Se NMR spectrum, it is evident that these NHC ligands possess rather poor π‐acidity.

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N-Propargylation and Copper(I)-Catalyzed Azide-Alkyne Cycloaddition as a Convenient Strategy for Directed Post-Synthetic Modification of 4-Oxo-1,4-Dihydrocinnoline Derivatives

Cited by 9 publications

References 47 publications

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Azides in the Synthesis of Various Heterocycles

Transition Metal Complexes of NHC Ligands Functionalized with the Cationic (η⁵‐Cyclopentadienyl)(η⁶‐phenyl)iron(II) Motif

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N-Propargylation and Copper(I)-Catalyzed Azide-Alkyne Cycloaddition as a Convenient Strategy for Directed Post-Synthetic Modification of 4-Oxo-1,4-Dihydrocinnoline Derivatives

Cited by 9 publications

References 47 publications

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Azides in the Synthesis of Various Heterocycles

Transition Metal Complexes of NHC Ligands Functionalized with the Cationic (η5‐Cyclopentadienyl)(η6‐phenyl)iron(II) Motif

Contact Info

Product

Resources

About

Transition Metal Complexes of NHC Ligands Functionalized with the Cationic (η⁵‐Cyclopentadienyl)(η⁶‐phenyl)iron(II) Motif