CuSO<sub>4</sub>–Glucose for in Situ Generation of Controlled Cu(I)–Cu(II) Bicatalysts: Multicomponent Reaction of Heterocyclic Azine and Aldehyde with Alkyne, and Cycloisomerization toward Synthesis of N-Fused Imidazoles

Guchhait, Sankar K.; Chandgude, Ajay L.; Priyadarshani, Garima

doi:10.1021/jo3003024

Cited by 160 publications

(51 citation statements)

References 34 publications

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“…To the best of our knowledge, d ‐glucose has been used rarely as a reducing agent in organic chemistry. It has been reported for the one‐pot assembly of N‐fused imidazoles, the reductive homocoupling of aryl halides, and the formation of quinolines involving a three‐steps cascade . Therefore, this seems to be the first report of the use of d ‐glucose as a reducing agent in a copper‐catalyzed reaction in an aqueous medium.…”

Section: Resultsmentioning

confidence: 76%

d‐Glucose: An Efficient Reducing Agent for a Copper(II)‐Mediated Arylation of Primary Amines in Water

et al. 2016

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A copper-catalyzed Ullmann-type amination with primary amines in water with a combination of copper(II) triflate [Cu(OTf) ], dipivaloylmethane, and d-glucose is reported. The mild conditions and the use of an inexpensive catalyst as well as a renewable feedstock (d-glucose and the surfactant TPGS-750-M, which is derived from vitamin E) make this protocol a safe and convenient strategy for efficient C-N bond formation. This easy-to-handle procedure is extremely competitive compared to palladium-based reactions and may be used to synthesize N-containing molecules, such as drugs or organic light-emitting diodes (OLEDs).

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Section: Resultsmentioning

confidence: 76%

d‐Glucose: An Efficient Reducing Agent for a Copper(II)‐Mediated Arylation of Primary Amines in Water

et al. 2016

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“…Coinage metal (Cu, Ag, or Au) catalyst could be crucial for A 3 -coupling and the cycloisomerization with electrophilic activation of alkyne. 11 Cu(I) halide as catalyst was preferentially chosen because of its known SYNLETT 2012SYNLETT , 23, 1955SYNLETT -1959 Advanced online publication: 23.07.20120 9 3 6 -5 2 1 4 1 4 3 7 -2 0 9 6 DOI: 10.1055/s-0032-1316606; Art ID: ST-2012-B0400-L © Georg Thieme Verlag Stuttgart · New York efficiency as a π-Lewis acid and less cost. 4-Chlorobenzaldehyde, benzylamine, phenylacetylene, and benzyl isocyanate were used as model substrates.…”

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confidence: 99%

One-Pot, Three-Step Copper-Catalyzed Five-/Four-Component Reaction Constructs Polysubstituted Oxa(Thia)zolidin-2-imines

Madaan¹,

Saraf²,

Priyadarshani³

et al. 2012

Synlett

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A novel one-pot synthesis of polysubstituted oxa(thia)zolidin-2-imines has been developed. It employs A 3 -coupling of aldehyde and amine with alkyne to form propargyl amine, which on (thio)amidation with iso(thio)cyanate produces N-propargyl(thio)urea, and a cyclization reaction. A 5-exo-dig iodocyclization of N-propargylurea constructs 5-iodomethyleneoxazolidin-2-imine, while cycloisomerization of the thio analogue provides 5-methylenethiazolidin-2-imine. In this process, CuI catalysis has been found to be crucial, and the cyclization occurs through oxygen/sulfur (not nitrogen) nucleophilic attack to alkyne.The major prescription drugs contain heterocyclic scaffolds. The crucial role played by heterocycles in drug-discovery processes has long been known. 1 Recent in silico investigations on drug database toward exploration of potential 'bioactivity islands' have revealed the importance of heterocyclic scaffolds. 2 The rapid and molecular-diversity-feasible construction of new and 'privileged' heterocyclic scaffolds has gained importance. In this direction, the amalgamation of a multicomponent reaction 3,4 and a consecutive one-pot process (domino, cascade, or tandem), 5 which in many cases gains efficiency under transition-metal catalysis, 6 is a golden nugget for the rapid construction of polysubstituted molecular scaffolds with atom-, step-, and pot-economy. 7 In this approach, variation in reactants can also generate a large number of compounds. As part of our research program aimed at realizing new leads, we became interested in developing a one-pot, multicomponent reaction that could afford pharmaceutically significant heterocyclic scaffolds. We speculated that a sequence of reactions of a multicomponent condensation of aldehyde, amine, and alkyne (A 3 -coupling) to form propargyl amine, 8 which on amidation produces Npropargylurea, whose endo-or exo-dig cycloisomerization with alkyne in the terminal step could produce dihydropyrimidinone I or imidazolidinone, respectively (Scheme 1). The later scaffold via isomerization of the double bond might possibly form the aromatic compound imidazolone II. Based on known therapeutic importance of these scaffolds 9,10 and the potential efficiency of the synthetic approach, we were interested in exploring the reaction sequence. A one-pot version of this synthesis, which was our endeavor also, is more challenging, because the process requires the catalyst and conditions compatibility and considerably high conversion in each reaction step. Coinage metal (Cu, Ag, or Au) catalyst could be crucial for A 3 -coupling and the cycloisomerization with electrophilic activation of alkyne. 11 Cu(I) halide as catalyst was preferentially chosen because of its known

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“…Guchhait et al . have explored the catalytic efficiency of mixed Cu(I)−Cu(II) system in situ generated by partial reduction of CuSO 4 with glucose in ethanol under open air for the three‐component reaction of heterocyclic azine and aldehyde with alkyne and cycloisomerization towards N‐fused imidazoles . Lee et al .…”

Section: Introductionmentioning

confidence: 99%

Heterogeneous Copper‐Catalyzed Cascade Three‐Component Reaction Towards Imidazo[1,2‐a]pyridines: Efficient and Practical One‐Pot Synthesis of Alpidem

Liao

Huang

et al. 2019

ChemistrySelect

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The heterogeneous cascade three-component reaction of 2aminopyridines, aldehydes and terminal alkynes was achieved in toluene at 120°C in the presence of 3-(2-aminoethylamino) propyl-functionalized MCM-41-immobilized copper(I) complex [MCM-41-2 N-CuCl] (5 mol%) and copper(II) complex [MCM-41-2NÀ Cu(OTf) 2 ] (5 mol%), yielding a wide variety of imidazo [1,2-a] pyridines in mostly good to excellent yields. These two heterogeneous copper catalysts can be facilely prepared via a simple procedure from readily available and inexpensive reagents, and recovered by filtration and recycled up to eight times with almost consistent activity. Figure 1. Imidazo[1,2-a]pyridine-based drug molecules.

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CuSO₄–Glucose for in Situ Generation of Controlled Cu(I)–Cu(II) Bicatalysts: Multicomponent Reaction of Heterocyclic Azine and Aldehyde with Alkyne, and Cycloisomerization toward Synthesis of N-Fused Imidazoles

Cited by 160 publications

References 34 publications

d‐Glucose: An Efficient Reducing Agent for a Copper(II)‐Mediated Arylation of Primary Amines in Water

d‐Glucose: An Efficient Reducing Agent for a Copper(II)‐Mediated Arylation of Primary Amines in Water

One-Pot, Three-Step Copper-Catalyzed Five-/Four-Component Reaction Constructs Polysubstituted Oxa(Thia)zolidin-2-imines

Heterogeneous Copper‐Catalyzed Cascade Three‐Component Reaction Towards Imidazo[1,2‐a]pyridines: Efficient and Practical One‐Pot Synthesis of Alpidem

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CuSO4–Glucose for in Situ Generation of Controlled Cu(I)–Cu(II) Bicatalysts: Multicomponent Reaction of Heterocyclic Azine and Aldehyde with Alkyne, and Cycloisomerization toward Synthesis of N-Fused Imidazoles

Cited by 160 publications

References 34 publications

d‐Glucose: An Efficient Reducing Agent for a Copper(II)‐Mediated Arylation of Primary Amines in Water

d‐Glucose: An Efficient Reducing Agent for a Copper(II)‐Mediated Arylation of Primary Amines in Water

One-Pot, Three-Step Copper-Catalyzed Five-/Four-Component Reaction Constructs Polysubstituted Oxa(Thia)zolidin-2-imines

Heterogeneous Copper‐Catalyzed Cascade Three‐Component Reaction Towards Imidazo[1,2‐a]pyridines: Efficient and Practical One‐Pot Synthesis of Alpidem

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CuSO₄–Glucose for in Situ Generation of Controlled Cu(I)–Cu(II) Bicatalysts: Multicomponent Reaction of Heterocyclic Azine and Aldehyde with Alkyne, and Cycloisomerization toward Synthesis of N-Fused Imidazoles