An Experimental and Theoretical Study of the 1,3-Dipolar Cycloaddition of Alloxan-Derived Azomethine Ylides to Cyclopropenes

Synthesis ◽  
2021 ◽  
Author(s):  
Alexander Vladimirovich Stepakov ◽  
Vitali Boitsov ◽  
Alexander Filatov ◽  
Stanislav Selivanov ◽  
Stanislav Shmakov ◽  
...  
Keyword(s):  
Density Functional ◽  
Theoretical Study ◽  
Azomethine Ylides ◽  
Dipolar Cycloaddition ◽  
Diastereoselective Synthesis ◽  
K562 Cell Line ◽  
Functional Theory ◽  
Shed Light ◽  
Mts Assay

A diastereoselective synthesis of biologically interesting spirobarbiturates has been achieved via [3 + 2] cycloaddition of alloxan-derived azomethine ylides to 3-R-1,2-diphenylcyclopropenes. With this approach, various spirobarbiturate-3-azabicyclo[3.1.0]hexanes and spirobarbiturate-cyclopropa[a]pyrrolizines were obtained in moderate to good yields with excellent diastereoselectivities. DFT calculations (M11 density functional theory) have been carried out to shed light on the molecular mechanism of 1,3-dipolar cycloaddition of alloxan-derived azomethine ylides to cyclopropenes. The cytotoxic activity of some obtained compounds against human erythroleukemia (K562) cell line was evaluated in vitro by MTS-assay.

Construction of Spiro[3-azabicyclo[3.1.0]hexanes] via 1,3-Dipolar Cycloaddition of 1,2-Diphenylcyclopropenes to Ninhydrin-Derived Azomethine Ylides

Synthesis ◽  
2021 ◽  
Author(s):  
Vitali M. Boitsov ◽  
Alexander V. Stepakov ◽  
Siqi Wang ◽  
Alexander S. Filatov ◽  
Stanislav V. Lozovskiy ◽  
...  
Keyword(s):  
Amino Acids ◽  
Density Functional ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Easy Access ◽  
Dipolar Cycloaddition ◽  
Functional Theory ◽  
Dimerization Reaction ◽  
High Degree

AbstractThe multi-component 1,3-dipolar cycloaddition of ninhydrin, α-amino acids (or peptides), and cyclopropenes for the synthesis of spirocyclic heterocycles containing both 3-azabicyclo[3.1.0]hexane and 2H-indene-1,3-dione motifs has been developed. This method provides easy access to 3-azabicyclo[3.1.0]hexane-2,2′-indenes with complete stereoselectivity and a high degree of atom economy under mild reaction conditions. A broad range of cyclopropenes and α-amino acids have been found to be compatible with the present protocol, which offers an opportunity to create a new library of biologically significant scaffold (3-azabicyclo[3.1.0]hexane). In addition, the сomprehensive study of mechanism of azomethine ylide formation from ninhydrin and sarcosine was performed by means of M11 density functional theory (DFT) calculations. It has been revealed that experimentally observed 1-methylspiro[aziridine-2,2′-indene]-1′,3′-dione is a kinetically controlled product of this reaction and appears to act as a 1,3-dipole precursor. This theoretical study also shed light on the main transformations of the azomethine ylide derived from ninhydrin and sarcosine such as a 1,3-dipolar cycloaddition to cyclopropene dipolarophiles, a dimerization reaction and a (1+5) electrocyclization reaction. The antitumor activity of some synthesized compounds against cervical carcinoma (HeLa­) cell line was evaluated in vitro by MTS-assay.

scholarly journals A General Pyrrolidine Synthesis via Iridium-Catalyzed Reductive Azomethine Ylide Generation from Tertiary Amides & Lactams

2021 ◽  
Author(s):  
Ken Yamazaki ◽  
Pablo Gabriel ◽  
Graziano Di Carmine ◽  
Julia Pedroni ◽  
Mirxan Farizyan ◽  
...  
Keyword(s):  
Density Functional ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Cycloaddition Reactions ◽  
Reaction Conditions ◽  
Functional Theory ◽  
Efficient Access ◽  
Stabilized Azomethine Ylides ◽  
Tertiary Amides

A new iridium-catalyzed reductive generation of both stabilized and unstabilized azomethine ylides and their application to functionalized pyrrolidine synthesis via [3+2] dipolar cycloaddition reactions is described. Proceeding under mild reaction conditions from both amide and lactam precursors possessing a suitably positioned electron-withdrawing or a trimethylsilyl group, using catalytic Vaska’s complex [IrCl(CO)(PPh3)2] and tetramethyldisiloxane (TMDS) as a terminal reductant, a broad range of (un)stabilized azomethine ylides were accessible. Subsequent, regio- and diastereoselective, inter- and intramolecular, dipolar cycloaddition reactions with variously substituted electron-poor alkenes enabled ready and efficient access to structurally complex pyrrolidine architectures. Density functional theory (DFT) calculations of the dipolar cycloaddition reactions uncovered an intimate balance between asynchronicity and interaction energies of transition structures which ultimately control the unusual selectivities observed in certain cases.

scholarly journals A General Pyrrolidine Synthesis via Iridium-Catalyzed Reductive Azomethine Ylide Generation from Tertiary Amides & Lactams

2021 ◽  
Author(s):  
Ken Yamazaki ◽  
Pablo Gabriel ◽  
Graziano Di Carmine ◽  
Julia Pedroni ◽  
Mirxan Farizyan ◽  
...  
Keyword(s):  
Density Functional ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Cycloaddition Reactions ◽  
Reaction Conditions ◽  
Functional Theory ◽  
Efficient Access ◽  
Stabilized Azomethine Ylides ◽  
Tertiary Amides

A new iridium-catalyzed reductive generation of both stabilized and unstabilized azomethine ylides and their application to functionalized pyrrolidine synthesis via [3+2] dipolar cycloaddition reactions is described. Proceeding under mild reaction conditions from both amide and lactam precursors possessing a suitably positioned electron-withdrawing or a trimethylsilyl group, using catalytic Vaska’s complex [IrCl(CO)(PPh3)2] and tetramethyldisiloxane (TMDS) as a terminal reductant, a broad range of (un)stabilized azomethine ylides were accessible. Subsequent, regio- and diastereoselective, inter- and intramolecular, dipolar cycloaddition reactions with variously substituted electron-poor alkenes enabled ready and efficient access to structurally complex pyrrolidine architectures. Density functional theory (DFT) calculations of the dipolar cycloaddition reactions uncovered an intimate balance between asynchronicity and interaction energies of transition structures which ultimately control the unusual selectivities observed in certain cases.

scholarly journals A General Pyrrolidine Synthesis via Iridium-Catalyzed Reductive Azomethine Ylide Generation from Tertiary Amides & Lactams

2021 ◽  
Author(s):  
Ken Yamazaki ◽  
Pablo Gabriel ◽  
Graziano Di Carmine ◽  
Julia Pedroni ◽  
Mirxan Farizyan ◽  
...  
Keyword(s):  
Density Functional ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Cycloaddition Reactions ◽  
Reaction Conditions ◽  
Functional Theory ◽  
Efficient Access ◽  
Stabilized Azomethine Ylides ◽  
Tertiary Amides

A new iridium-catalyzed reductive generation of both stabilized and unstabilized azomethine ylides and their application to functionalized pyrrolidine synthesis via [3+2] dipolar cycloaddition reactions is described. Proceeding under mild reaction conditions from both amide and lactam precursors possessing a suitably positioned electron-withdrawing or a trimethylsilyl group, using catalytic Vaska’s complex [IrCl(CO)(PPh3)2] and tetramethyldisiloxane (TMDS) as a terminal reductant, a broad range of (un)stabilized azomethine ylides were accessible. Subsequent, regio- and diastereoselective, inter- and intramolecular, dipolar cycloaddition reactions with variously substituted electron-poor alkenes enabled ready and efficient access to structurally complex pyrrolidine architectures. Density functional theory (DFT) calculations of the dipolar cycloaddition reactions uncovered an intimate balance between asynchronicity and interaction energies of transition structures which ultimately control the unusual selectivities observed in certain cases.

A THEORETICAL STUDY ON THE MECHANISM OF 2:1 1, 3 DIPOLAR CYCLOADDITION REACTIONS

2007 ◽  
Vol 06 (04) ◽  
pp. 861-867 ◽  
Author(s):  
JING-FANG WANG ◽  
DONG-QING WEI ◽  
CHUN-FANG WANG ◽  
YONG YE ◽  
YI-XUE LI ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Organic Synthesis ◽  
Density Functional ◽  
Theoretical Study ◽  
Cycloaddition Reaction ◽  
Density Functional Theory Calculations ◽  
Biologically Active ◽  
Dipolar Cycloaddition ◽  
Functional Theory ◽  
Nitrile Oxides

The reactions between nitrile oxides and alkenes are of considerable interest in organic synthesis as the resulting heterocycles are versatile intermediates for the synthesis of natural products and biologically active compounds. In this paper, we design a series of reactions of phosphonyl nitrile oxides with acrylonnitrile, which can give 2:1 cycloaddition products with no crystal structure released so far, and present a detailed theoretical study on the mechanism of the 2:1 1, 3-dipolar cycloaddition reaction, which has been explored with density functional theory calculations at B3LYP/6-31G* level. The results reveal that the following mechanism is quite possible. Firstly, it starts as a normal 1,3-dipolar cycloaddition reaction to produce a regiospecific 1:1 product. Subsequently, highly reactive diisopropanyl phosphonyl nitrile oxide sequentially reacts with the aforementioned regiospecific 1:1 product and gives the corresponding cycloadduct. Further study is underway to expand the scope of this methodology, as well as to ascertain mechanistic details of the cycloaddition process.

scholarly journals Theoretical Study of Zirconium Isomorphous Substitution into Zeolite Frameworks

Molecules ◽  
2019 ◽  
Vol 24 (24) ◽  
pp. 4466
Author(s):  
Duichun Li ◽  
Bin Xing ◽  
Baojun Wang ◽  
Ruifeng Li
Keyword(s):  
Acid Site ◽  
Density Functional ◽  
Theoretical Study ◽  
Atomic Radius ◽  
Acid Sites ◽  
Isomorphous Substitution ◽  
Dispersion Correction ◽  
Brønsted Acidity ◽  
Functional Theory ◽  
Brönsted Acidity

Systematic periodic density functional theory computations including dispersion correction (DFT-D) were carried out to determine the preferred location site of Zr atoms in sodalite (SOD) and CHA-type topology frameworks, including alumino-phosphate-34 (AlPO-34) and silico-alumino-phosphate-34 (SAPO-34), and to determine the relative stability and Brönsted acidity of Zr-substituted forms of SOD, AlPO-34, and SAPO-34. Mono and multiple Zr atom substitutions were considered. The Zr substitution causes obvious structural distortion because of the larger atomic radius of Zr than that of Si, however, Zr-substituted forms of zeolites are found to be more stable than pristine zeolites. Our results demonstrate that in the most stable configurations, the preferred favorable substitutions of Zr in substituted SOD have Zr located at the neighboring sites of the Al-substituted site. However, in the AlPO-34 and SAPO-34 frameworks, the Zr atoms are more easily distributed in a dispersed form, rather than being centralized. Brönsted acidity of substituted zeolites strongly depends on Zr content. For SOD, substitution of Zr atoms reduces Brönsted acidity. However, for Zr-substituted forms of AlPO-34 and SAPO-34, Brönsted acidity of the Zr-O(H)-Al acid sites are, at first, reduced and, then, the presence of Zr atoms substantially increased Brönsted acidity of the Zr-O(H)-Al acid site. The results in the SAPO-34-Zr indicate that more Zr atoms substantially increase Brönsted acidity of the Si-O(H)-Al acid site. It is suggested that substituted heteroatoms play an important role in regulating and controlling structural stability and Brönsted acidity of zeolites.

The 1,3-dipolar cycloaddition of 1H-pyridinium-3-olate and 1-methylpyridinium-3-olate with methyl acrylate: a density functional theory study

Tetrahedron ◽  
2010 ◽  
Vol 66 (47) ◽  
pp. 9187-9193 ◽  
Author(s):  
Lydia Rhyman ◽  
Hassan H. Abdallah ◽  
Sabina Jhaumeer-Laulloo ◽  
Luis R. Domingo ◽  
John A. Joule ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Methyl Acrylate ◽  
Density Functional ◽  
Dipolar Cycloaddition ◽  
Density Functional Theory Study ◽  
Functional Theory

Structure, stability and intramolecular interaction of M(N5)2(M = Mg, Ca, Sr and Ba) : a theoretical study

RSC Advances ◽  
2015 ◽  
Vol 5 (28) ◽  
pp. 21823-21830 ◽  
Author(s):  
Xueli Zhang ◽  
Junqing Yang ◽  
Ming Lu ◽  
Xuedong Gong
Keyword(s):  
Energetic Materials ◽  
Density Functional ◽  
Alkaline Earth ◽  
Theoretical Study ◽  
Intramolecular Interaction ◽  
Earth Metal ◽  
Structure Stability ◽  
Alkaline Earth Metal ◽  
Functional Theory ◽  
The Density Functional Theory

The potential energetic materials, alkaline earth metal complexes of the pentazole anion (M(N5)2, M = Mg2+, Ca2+, Sr2+and Ba2+), were studied using the density functional theory.

Study of the Stability and Chemical Reactivity of a Series of Tetrazole Pyrimidine Hybrids by the Density Functional Theory Method (DFT)

2021 ◽  
Vol 37 (4) ◽  
pp. 805-812
Author(s):  
Ahissandonatien Ehouman ◽  
Adjoumanirodrigue Kouakou ◽  
Fatogoma Diarrassouba ◽  
Hakim Abdel Aziz Ouattara ◽  
Paulin Marius Niamien
Keyword(s):  
Density Functional ◽  
Theoretical Study ◽  
Molecular Descriptors ◽  
Chemical Reactivity ◽  
Density Functional Theory Method ◽  
Functional Theory ◽  
Reactivity Descriptors ◽  
The Density Functional Theory ◽  
The Stability ◽  
Global Reactivity Descriptors

Our theoretical study of stability and reactivity was carried out on six (06) molecules of a series of pyrimidine tetrazole hybrids (PTH) substituted with H, F, Cl, Br, OCH3 and CH3 atoms and groups of atoms using the density function theory (DFT). Analysis of the thermodynamic formation quantities confirmed the formation and existence of the series of molecules studied. Quantum chemical calculations at the B3LYP / 6-311G (d, p) level of theory determined molecular descriptors. Global reactivity descriptors were also determined and analyzed. Thus, the results showed that the compound PTH_1 is the most stable, and PTH_5 is the most reactive and nucleophilic. Similarly, the compound PTH_4 is the most electrophilic. The analysis of the local descriptors and the boundary molecular orbitals allowed us to identify the preferred atoms for electrophilic and nucleophilic attacks.

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