Concise Synthesis of Tryptanthrin Spiro Analogues with In Vitro Antitumor Activity Based on One-Pot, Three-Component 1,3-Dipolar Cycloaddition of Azomethine Ylides to Сyclopropenes

Synthesis ◽  
2018 ◽  
Vol 51 (03) ◽  
pp. 713-729 ◽  
Author(s):  
Vitali Boitsov ◽  
Alexander Stepakov ◽  
Alexander Filatov ◽  
Nickolay Knyazev ◽  
Stanislav Shmakov ◽  
...  
Keyword(s):  
Antitumor Activity ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
One Pot ◽  
Economic Method ◽  
Reaction Proceeds ◽  
High Yields

A simple, efficient and atom-economic method has been developed for the synthesis of complex alkaloid-like compounds with spiro-fused indolo[2,1-b]quinazoline and cyclopropa[a]pyrrolizine or 3-azabicyclo[3.1.0]hexane moieties. We have found that one-pot, three-component 1,3-dipolar cycloaddition reactions allow the desired products to be obtained from various cyclopropene derivatives with tryptanthrin-derived azomethine ylides generated in situ, in good to high yields and excellent diastereoselectivity. The possibility of ylide generation was exemplified by using α-amino acids (l-proline, l-4-thiazolidincarboxylic acid) and simplest peptides (dipeptide Gly-Gly, tripeptide Gly-Gly-Gly). Quantum chemical investigations indicate that the reaction proceeds through the S-shaped azomethine ylide, the interaction of which with cyclopropenes proceeds via a less sterically hindered endo-transition state. The antitumor activity of some of spiro-tryptanthrin derivatives against erythroleukemia (K562), cervical carcinoma (HeLa) and colon carcinoma (CT26) cell lines was evaluated in vitro by MTS-assay.

Reactions of 4-Pyrones with Azomethine Ylides as a Chemo­selective Method for the Construction of Multisubstituted Pyrano[2,3-c]pyrrolidines

Synthesis ◽  
2021 ◽  
Author(s):  
Dmitrii L. Obydennov ◽  
Vyacheslav D. Steben’kov ◽  
Konstantin L. Obydennov ◽  
Sergey A. Usachev ◽  
Vladimir S. Moshkin ◽  
...  
Keyword(s):  
Double Bond ◽  
Ring Opening ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Computational Studies ◽  
Carbon Double Bond ◽  
Reactivity Indexes ◽  
Reaction Proceeds

Abstract4-Pyrones bearing electron-donating and electron-withdrawing groups react with nonstabilized azomethine ylides to form pyrano[2,3-c]pyrrolidines in moderate to good yields. The reaction proceeds chemoselectively as a 1,3-dipolar cycloaddition of the azomethine ylide at the carbon–carbon double bond of the pyrone activated by the electron-withdrawing substituent. The reactivity of 4-pyrones toward azomethine ylides was rationalized by computational studies with the use of reactivity indexes. The pyrano[2,3-c]pyrrolidine moiety could be modified, for example by a ring-opening transformation under the action of hydrazine to provide pyrazolyl-substituted pyrrolidines.

Highly Selective One-Pot Synthesis of Polysubstituted Isoflavanes using Styryl Ethers and Electron-Withdrawing ortho-Quinone Methides Generated In Situ

Synlett ◽  
2018 ◽  
Vol 30 (02) ◽  
pp. 189-192 ◽  
Author(s):  
Yujiro Hoshino ◽  
Kiyoshi Honda ◽  
Kenta Tanaka ◽  
Mami Kishimoto ◽  
Naoya Ohtsuka ◽  
...  
Keyword(s):  
Biologically Active ◽  
Quinone Methides ◽  
One Pot ◽  
One Pot Synthesis ◽  
Reaction Proceeds ◽  
Acidic Conditions ◽  
High Yields

A highly selective one-pot synthesis of polysubstituted isoflavanes has been developed. The reaction proceeds through the cycloaddition of methyl styryl ethers, derived from phenylacetaldehyde dimethyl acetals under acidic conditions, with electron-withdrawing ortho-quinone methides generated in situ. When phenylacetaldehyde dimethyl acetals were reacted with salicylaldehydes, the reaction proceeded smoothly to afford the corresponding isoflavanes stereoselectively in high yields and with excellent regioselectivities. The present reaction provides versatile access to functionalized isoflavanes, and constitutes a useful tool for the synthesis of biologically active molecules.

Azomethine Ylide Cycloaddition of 1,3- dienyl esters: Highly regio- and diastereoselective synthesis of functionalized pyrrolidinochromenes

2022 ◽  
Author(s):  
Manickam Bakthadoss ◽  
Mohammad Mushaf ◽  
Vishal Agarwal ◽  
Tadiparthi Thirupathi Reddy ◽  
Duddu Savaraiah Sharada
Keyword(s):  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Diastereoselective Synthesis

An efficient protocol for the synthesis of tricyclic pyrolidinochromenes has been developed via an intramolecular 1,3-dipolar cycloaddition of azomethine ylides generated in situ from 1,3- dienyl ester tethered O-hydroxyarylaldehyde and...

Diastereoselective synthesis of indolenine-based spiro[pyrazolone-4,2’-pyrrolidine] scaffolds via 1,3-dipolar cycloaddition of 4-aminopyrazolones, aldehydes, and indolenines

2021 ◽  
Author(s):  
Baomin Wang ◽  
Shah Nawaz ◽  
Shiqiang Wei ◽  
Yue Huang ◽  
Wenyao Wang ◽  
...  
Keyword(s):  
Azomethine Ylides ◽  
Dipolar Cycloaddition ◽  
Diastereoselective Synthesis ◽  
One Pot

In this work, we report a novel one-pot [3+2] cycloaddition of 4-aminopyrazolones, indolenines, and aldehydes. The reaction utilized the in-situ generated azomethine ylides as 1,3-dipoles and 2-alkenylindolenines as dipolarophiles affording...

scholarly journals Multicomponent synthesis of spiropyrrolidine analogues derived from vinylindole/indazole by a 1,3-dipolar cycloaddition reaction

2016 ◽  
Vol 12 ◽  
pp. 2893-2897 ◽  
Author(s):  
Manjunatha Narayanarao ◽  
Lokesh Koodlur ◽  
Vijayakumar G Revanasiddappa ◽  
Subramanya Gopal ◽  
Susmita Kamila
Keyword(s):  
Amino Acids ◽  
Cycloaddition Reaction ◽  
Thermal Conditions ◽  
Azomethine Ylides ◽  
Dipolar Cycloaddition ◽  
Side Chains ◽  
Multicomponent Synthesis ◽  
One Pot ◽  
Cyclic Adducts

A new series of spiropyrrolidine compounds containing indole/indazole moieties as side chains have been accomplished via a one-pot multicomponent synthesis. The method uses the 1,3-dipolar cycloaddition reaction between N-alkylvinylindole/indazole and azomethine ylides, prepared in situ from cyclic/acyclic amino acids. The 1,3-dipolar cycloaddition proceeds efficiently under thermal conditions to afford the regio- and stereospecific cyclic adducts.

scholarly journals Synthesis of pyrrolizidines and indolizidines by multicomponent 1,3-dipolar cycloaddition of azomethine ylides

2019 ◽  
Vol 91 (4) ◽  
pp. 575-596 ◽  
Author(s):  
Carmen Nájera ◽  
José Miguel Sansano
Keyword(s):  
Amino Acid ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Amino Acid Derivatives ◽  
Reaction Conditions ◽  
Dipolar Cycloadditions ◽  
Spiro Derivatives ◽  
Stabilized Azomethine Ylides

Abstract Different multicomponent 1,3-dipolar cycloadditions (1,3-DC) of cyclic α-amino acid derivatives with aldehydes and dipolarophiles have been described as efficient and simple methodologies for the synthesis of the pyrrolidine unit of pyrrolizidines and indolizidines. When free cyclic α-amino acids are used, a thermal promoted decarboxylative process generates in situ the corresponding non-stabilized azomethine ylides, which afforded the corresponding pyrrolizidines and indolizidines with a hydrogen in the bicyclic units. This methodology has been employed to the synthesis of complex systems including spiro derivatives when ketones are used as carbonyl component. In addition, working with cyclic α-amino acid derived esters, the three-component 1,3-DC takes place under milder reaction conditions giving the corresponding pyrrolizidines and indolizidines with an alkoxycarbonyl group in the bridge adjacent carbon to the nitrogen. This methodology can be carried out by a double consecutive or stepwise 1,3-DC to provide pyrrolizidines via the precursor prolinates. The conformation of the azomethine ylide controls the endo/exo diastereoselectivity of the 1,3-DC.

scholarly journals Endo-Selective Construction of Spiro-[butyrolactone-pyrrolidine] via Ag(I)/CAAA-Amidphos-Catalyzed 1,3-Dipolar Cycloaddition between Azomethine Ylides and α-Methylene-γ-Butyrolactone

Catalysts ◽  
2019 ◽  
Vol 10 (1) ◽  
pp. 28 ◽  
Author(s):  
Qinglin Hou ◽  
Yaoyao You ◽  
Xinluo Song ◽  
Yingxia Wang ◽  
Ke Chen ◽  
...  
Keyword(s):  
Organic Chemistry ◽  
Catalytic System ◽  
Azomethine Ylides ◽  
Dipolar Cycloaddition ◽  
Effective Strategy ◽  
Optimal Conditions ◽  
One Pot ◽  
Synthetic Organic Chemistry ◽  
Quaternary Stereocenter

Construction of spirocyclic pyrrolidines bearing a spiro quaternary stereocenter is an enormous challenge in synthetic organic chemistry. In this report, we introduce a Ag(I)/CAAA-amidphos-catalyzed enantioselective 1,3-dipolar cycloaddition between azomethine ylides and α-methylene-γ-butyrolactone as an effective strategy for the construction of excellent endo-selective spiro-[butyrolactone-pyrrolidine] derivatives. Meanwhile, the catalytic system was also successfully applied in the three-component one-pot reaction of azomethine ylides formed in situ under the action of N,N′-diisopropylcarbodiimide serving as a dehydrator. Under the optimal conditions, endo-pyrrolidine derivatives bearing a spiro quaternary stereocenter were obtained with high to excellent yields (up to 95% yield) and enantioselectivities (up to 93% ee).

scholarly journals An effective one-pot access to polynuclear dispiroheterocyclic structures comprising pyrrolidinyloxindole and imidazothiazolotriazine moieties via a 1,3-dipolar cycloaddition strategy

2016 ◽  
Vol 12 ◽  
pp. 2240-2249 ◽  
Author(s):  
Alexei N Izmest’ev ◽  
Galina A Gazieva ◽  
Natalya V Sigay ◽  
Sergei A Serkov ◽  
Valentina A Karnoukhova ◽  
...  
Keyword(s):  
Azomethine Ylides ◽  
Dipolar Cycloaddition ◽  
One Pot ◽  
Stereogenic Centers ◽  
Isatin Derivatives

An effective and highly regio- and diastereoselective one-pot method for the synthesis of new polynuclear dispiroheterocyclic systems with five stereogenic centers (dispiro[imidazo[4,5-e]thiazolo[3,2-b]-1,2,4-triazine-6,3′-pyrrolidine-2′,3′′-indoles]) comprising pyrrolidinyloxindole and imidazo[4,5-e]thiazolo[3,2-b]-1,2,4-triazine moieties has been developed. The method relies on a 1,3-dipolar cycloaddition of azomethine ylides generated in situ from isatin derivatives and sarcosine to 6-benzylideneimidazo[4,5-e]thiazolo[3,2-b]-1,2,4-triazine-2,7-diones.

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