Synthesis of difluoroboron adamantyl-containing complexes and pyrazoles based thereon

Коньков, С. А.; Krylov, K. S.; Бормашева, К. М.; Моисеев, И. К.

doi:10.1134/s1070428014110165

Cited by 5 publications

(6 citation statements)

References 4 publications

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“…Starting 5‐(1‐adamantyl)‐3‐methyl‐1 H ‐pyrazole can be prepared with high yield via the reaction of 1‐(1‐adamantyl)butane‐1,3‐dione with hydrazine hydrate according to a published protocol [15] . Thereafter, this pyrazole was quantitatively converted to bis(pyrazolyl)methane via the reaction with dibromomethane in the presence of potassium hydroxide and potassium carbonate in refluxing dichloromethane according to Scheme 2.…”

Section: Resultsmentioning

confidence: 99%

“…Mass spectra were obtained with the mass spectrometer Finnigan MAT SSQ 710. Starting 5‐(1‐adamantyl)‐3‐methyl‐1 H ‐pyrazole was prepared according to a literature protocol [15] …”

Section: Methodsmentioning

confidence: 99%

“…Starting 5-(1-adamantyl)-3-methyl-1H-pyrazole was prepared according to a literature protocol. [15] Synthesis of (tetrahydrofuran)lithium 1,1-bis(3,5-dimethylpyrazolyl)-2,2-diphenyl-2-ethyl-cyclopentadienide, [(thf)Li{CpÀ CPh 2 À CHPz Me2 }] (1 a). The synthesis of 1 a was performed according to a literature procedure.…”

Section: Methodsmentioning

confidence: 99%

“…Starting 5-(1-adamantyl)-3-methyl-1H-pyrazole can be prepared with high yield via the reaction of 1-(1-adamantyl)butane-1,3dione with hydrazine hydrate according to a published protocol. [15] Thereafter, this pyrazole was quantitatively converted to bis(pyrazolyl)methane via the reaction with dibromomethane in the presence of potassium hydroxide and potassium carbonate in refluxing dichloromethane according to Scheme 2. Different substituents in 3-and 5-positions of the pyrazole substrate led to a mixture of three different isomers of bis(3,5-dialkylpyrazolyl)methane: bis(3-adamantyl-5-methylpyrazolyl)methane (H 2 C(Pz Ad,Me ) 2 , 2 a, 42 %), bis(3-methyl-5adamantylpyrazolyl)methane (H 2 C(Pz Me,Ad ) 2 , 2 c, 11 %) and the mixed isomer (3-adamantyl-5-methylpyrazolyl)-(3-methyl-5adamantylpyrazolyl)methane ((H 2 C(Pz Ad,Me )(Pz Me,Ad ), 2 b, 47 %).…”

Section: Synthesesmentioning

confidence: 99%

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Synthesis and Structure of a New Bulky Hybrid Scorpionate/Cyclopentadienyl Ligand and its Lithium Complex

Westerhausen

Miles²,

Görls³

2022

Zeitschrift anorg allge chemie

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The reaction of 5‐(1‐adamantyl)‐3‐methyl‐1H‐pyrazole with dibromomethane yields a product mixture of bis(3‐adamantyl‐5‐methylpyrazolyl)methane (H2C(PzAd,Me)2, 2 a), (3‐adamantyl‐5‐methylpyrazolyl)‐(3‐methyl‐5‐adamantylpyrazolyl)methane ((H2C(PzAd,Me)(PzMe,Ad), 2 b) and bis(3‐methyl‐5‐adamantylpyrazolyl)methane (H2C(PzMe,Ad)2, 2 c). Lithiation of sterically congested H2C(PzAd,Me)2 (2 a) and subsequent addition of diphenylfulvene yields lithium 1,1‐bis(3‐adamantyl‐5‐methylpyrazolyl)‐2,2‐diphenyl‐2‐ethyl‐cyclopentadienide, [(thf)Li{Cp−CPh2−CHPzAd,Me}] (3) which is unable to form a thf adduct but can be hydrolyzed to H5C5−CPh2−CHPzAd,Me (4). Adamantyl groups in 5‐position of bis(pyrazolyl)methane, i. e. 2 b and 2 c, prohibit formation of a fulvene adduct. For comparison reasons, [{H5C5−CPh2−CHPzMe2}LiI] (1 b) has been prepared via protolysis of (thf)lithium 1,1‐bis(3,5‐dimethylpyrazolyl)‐2,2‐diphenyl‐2‐ethyl‐cyclopentadienide, [(thf)Li{Cp−CPh2−CHPzMe2}] (1 a), in the presence of calcium iodide.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Synthesesmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and Structure of a New Bulky Hybrid Scorpionate/Cyclopentadienyl Ligand and its Lithium Complex

Westerhausen

Miles²,

Görls³

2022

Zeitschrift anorg allge chemie

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“…Literature procedures were used to prepare adamantane derivatives 2, 16 3a, 17 and 3b. 18 All the reactions were monitored by TLC performed on precoated silica gel plates (Sorbfil); compounds were made visual with I 2 . Melting points were measured using an OptiMelt Automated Melting Point System.…”

Section: Scheme 3 Reactions Of Adamantylated Pyrimidine-2-thione 7bmentioning

confidence: 99%

Synthesis of Adamantylated Pyrimidines Using the Biginelli Reaction

2016

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Using an adamantane 3-oxonitrile and adamantane 1,3-dicarbonyl compounds in the three-component Biginelli reaction promoted by trimethylsilyl chloride, adamantylated pyrimidines are prepared. The reaction with the oxonitrile leads to 6-(1-adamantyl)-2thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitriles and/or 2-benzylidene-3-oxonitriles depending on the type of aromatic aldehyde. 1,3-Dicarbonyl adamantane compounds give 1-adamantyl(2-thioxo-1,2,3,4-tetrahydropyrimidine-5-yl)methanones with low yields. An adamantylated 2-thioxo-1,2,3,4-tetrahydropyrimidine is used to prepare thiazolo[3,2-a]pyrimidine derivatives.

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Palladium‐Catalyzed Chemoselective Amination of Chloro(hetero)aryl Triflates Enabled by Alkyl‐Pyrazole‐Based Phosphine Ligands

Gu,

Yuen,

et al. 2024

Adv Synth Catal

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This study describes the palladium‐catalyzed chemoselective amination of chloro(hetero)aryl triflates in the C−Cl bond for the first time. A newly designed and synthesized alkyl‐pyrazole‐based phosphine ligand, <b>L26</b> (BirdPhos), which is featured with the pyrazole ligand core and the cyclohexyl group at the C3 and C5 positions, was key to the success of this reaction. A variety of chloro(hetero)aryl triflates coupled with aromatic, aliphatic, and heterocyclic amines smoothly afforded the corresponding products up to 97% yields with general chemoselectivity (>99%) in the C−Cl bond. Drug analogs were also synthesized via the chemoselective intermolecular amination. This study attempts to investigate the structure‐activity relationship of this new class of ligand through experimental and density functional theory (DFT) calculations.

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Synthesis of difluoroboron adamantyl-containing complexes and pyrazoles based thereon

Cited by 5 publications

References 4 publications

Synthesis and Structure of a New Bulky Hybrid Scorpionate/Cyclopentadienyl Ligand and its Lithium Complex

Synthesis and Structure of a New Bulky Hybrid Scorpionate/Cyclopentadienyl Ligand and its Lithium Complex

Synthesis of Adamantylated Pyrimidines Using the Biginelli Reaction

Palladium‐Catalyzed Chemoselective Amination of Chloro(hetero)aryl Triflates Enabled by Alkyl‐Pyrazole‐Based Phosphine Ligands

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