Straightforward Regio- and Diastereoselective Synthesis, Molecular Structure, Intermolecular Interactions and Mechanistic Study of Spirooxindole-Engrafted Rhodanine Analogs

Straightforward regio- and diastereoselective synthesis of bi-spirooxindole-engrafted rhodanine analogs 5a–d were achieved by one-pot multicomponent [3 + 2] cycloaddition (32CA) reaction of stabilized azomethine ylide (AYs 3a–d) generated in situ by condensation of L-thioproline and 6-chloro-isatin with (E)-2-(5-(4-chlorobenzylidene)-2,4-dioxothiazolidin-3-yl)-N-(2-morpholinoethyl)acetamide. The bi-spirooxindole-engrafted rhodanine analogs were constructed with excellent diastereo- and regioselectivity along with high chemical yield. X-ray crystallographic investigations for hybrid 5a revealed the presence of four contiguous stereocenters related to C11, C12, C19 and C22 of the spiro structure. Hirshfeld calculations indicated the presence of many short intermolecular contacts such as Cl...C, S...S, S...H, O...H, N...H, H...C, C...C and H...H interactions. These contacts played a very important role in the crystal stability. The polar nature of the 32CA reaction was studied by analysis of the conceptual DFT reactivity indices. Theoretical study of this 32CA reaction indicated that it takes place through a non-concerted two-stage one-step mechanism associated with the nucleophilic attack of AY 3a to the electrophilic ethylene derivative.

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Computational and experimental investigations of one-step conversion of poly(carbonate)s into value-added poly(aryl ether sulfone)s

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1600924113 ◽

2016 ◽

Vol 113 (28) ◽

pp. 7722-7726 ◽

Cited By ~ 29

Author(s):

Gavin O. Jones ◽

Alexander Yuen ◽

Rudy J. Wojtecki ◽

James L. Hedrick ◽

Jeannette M. García

Keyword(s):

High Performance ◽

Density Functional ◽

Value Added ◽

Single Step ◽

Nucleophilic Attack ◽

Experimental Investigations ◽

Aryl Ether ◽

One Step ◽

Poly Carbonate

It is estimated that ∼2.7 million tons poly(carbonate)s (PCs) are produced annually worldwide. In 2008, retailers pulled products from store shelves after reports of bisphenol A (BPA) leaching from baby bottles, reusable drink bottles, and other retail products. Since PCs are not typically recycled, a need for the repurposing of the PC waste has arisen. We report the one-step synthesis of poly(aryl ether sulfone)s (PSUs) from the depolymerization of PCs and in situ polycondensation with bis(aryl fluorides) in the presence of carbonate salts. PSUs are high-performance engineering thermoplastics that are commonly used for reverse osmosis and water purification membranes, medical equipment, as well as high temperature applications. PSUs generated through this cascade approach were isolated in high purity and yield with the expected thermal properties and represent a procedure for direct conversion of one class of polymer to another in a single step. Computational investigations performed with density functional theory predict that the carbonate salt plays two important catalytic roles in this reaction: it decomposes the PCs by nucleophilic attack, and in the subsequent polyether formation process, it promotes the reaction of phenolate dimers formed in situ with the aryl fluorides present. We envision repurposing poly(BPA carbonate) for the production of value-added polymers.

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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 ◽

10.1055/s-0037-1611059 ◽

2018 ◽

Vol 51 (03) ◽

pp. 713-729 ◽

Cited By ~ 6

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.

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A Novel One-step Synthesis of Quinoline-2(1H)-thiones and Selones by Treating 3-Aryl-3-(2-aminophenyl)-1-propyn-3-ols with a Base and Elemental Sulfur or Selenium

Natural Product Communications ◽

10.1177/1934578x1501000628 ◽

2015 ◽

Vol 10 (6) ◽

pp. 1934578X1501000 ◽

Cited By ~ 1

Author(s):

Kazuaki Shimada ◽

Hironori Izumi ◽

Koki Otashiro ◽

Kensuke Noro ◽

Shigenobu Aoyagi ◽

...

Keyword(s):

Elemental Sulfur ◽

Reactive Species ◽

Nucleophilic Attack ◽

Amino Group ◽

One Step ◽

High Yields

A one-step conversion of 3-aryl-3-(2-aminophenyl)-1-propyn-3-ols into quinoline-2(1 H)-thiones and quinoline-2(1 H)-selones was achieved only by treating the substrates with n-butyllithium and either elemental sulfur or selenium, respectively. The reactions were assumed to proceed through an intramolecular nucleophilic attack of the neighboring amino group to the plausible in situ generated reactive species related to chalcogenoketenes. The subsequent mCPBA oxidation of quinoline-2(1 H)-selones afforded quinolin-2(1 H)-ones in high yields.

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One-Step Synthesis of Acylboron Compounds via Cu-Catalyzed Carbonylative Borylation of Alkyl Halides

10.26434/chemrxiv.12818180 ◽

2020 ◽

Author(s):

Cheng Li-Jie ◽

Zhao Siling ◽

Neal Mankad

Keyword(s):

Alkyl Halides ◽

Efficient Synthesis ◽

Mechanistic Studies ◽

Acyl Halide ◽

Reaction Conditions ◽

One Pot ◽

One Step ◽

High Yields ◽

Tertiary Alkyl

A Cu-catalyzed carbonylative borylation of unactivated alkyl halides has been developed, enabling efficient synthesis of aliphatic potassium acyltrifluoroborates (KATs) in high yields by treating the in-situ formed tetracoordinated acylboron intermediates with aqueous KHF2. A variety of functional groups are tolerated under the mild reaction conditions, and primary, secondary and tertiary alkyl halides are all applicable. In addition, this method also provides facile access to N-methyliminodiacetyl (MIDA) acylboronates as well as α-methylated potassium acyltrifluoroborates in a one-pot manner. Mechanistic studies indicate a radical atom transfer carbonylation (ATC) mechanism to form acyl halide intermediates that are subsequently borylated by (NHC)CuBpin.<br>

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Highly Diastereoselective Synthesis of Tetrahydroquinoline Derivatives via [4 + 2] Annulation of Ortho-Tosylaminophenyl-Substituted Para-Quinone Methides and Cyanoalkenes

Frontiers in Chemistry ◽

10.3389/fchem.2021.764866 ◽

2021 ◽

Vol 9 ◽

Author(s):

Taiwei Dong ◽

Peifeng Wei ◽

Min Li ◽

Feng Gao ◽

Yuan Qin

Keyword(s):

Biologically Active ◽

Structural Motif ◽

Diastereoselective Synthesis ◽

Atom Economy ◽

Quinone Methides ◽

One Pot ◽

Reaction Performance ◽

High Yields ◽

Active Natural

As a privileged structural motif, tetrahydroquinoline skeletons widely exist in biologically active natural products and pharmaceuticals. In this protocol, a highly diastereoselective [4 + 2] annulation of ortho-tosylaminophenyl-substituted p-QMs and cyanoalkenes to construct tetrahydroquinoline derivatives has been successfully achieved. This strategy proceeds efficiently under mild condition, offering straightforward route to a variety of 4-aryl-substituted tetrahydroquinolines with high yields, excellent diastereoselectivities, broad functional group tolerance as well as gram-scale capacity. Moreover, a one-pot reaction sequence utilizing in situ generated p-QMs under the similar condition to build tetrahydroquinoline framework is smoothly conducted with good reaction performance as well as step and atom economy.

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1-(4-Nitrophenyl)-1H-1,2,3-Triazole-4-carbaldehyde: Scalable Synthesis and Its Use in the Preparation of 1-Alkyl-4-Formyl-1,2,3-triazoles

Organics ◽

10.3390/org2040024 ◽

2021 ◽

Vol 2 (4) ◽

pp. 404-414

Author(s):

Tomas Opsomer ◽

Kaat Valkeneers ◽

Ana Ratković ◽

Wim Dehaen

Keyword(s):

One Pot ◽

Complete Hydrolysis ◽

One Step ◽

Synthetic Intermediates ◽

Cornforth Rearrangement ◽

Scalable Synthesis ◽

The One ◽

Novel Applications ◽

Hydrolysis Of

1,2,3-Triazole-4-carbaldehydes are useful synthetic intermediates which may play an important role in the discovery of novel applications of the 1,2,3-triazole moiety. In this work, a one-step multigram scale synthesis of 4-formyl-1-(4-nitrophenyl)-1H-1,2,3-triazole (FNPT) as a preferred reagent for the synthesis of 1-alkyl-4-formyltriazoles is described, making use of the commercially available 3-dimethylaminoacrolein and 4-nitrophenyl azide. Next, the earlier reported reaction of FNPT with alkylamines is further explored, and for hexylamine, the one-pot sequential cycloaddition and Cornforth rearrangement is demonstrated. In addition, a useful protocol for the in situ diazotization of 4-nitroaniline is provided. This facilitated the complete hydrolysis of rearranged 4-iminomethyl-1,2,3-triazoles and allowed for the recycling of 4-nitrophenyl azide.

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CO2 coupling with epoxides catalysed by using one-pot synthesised, in situ activated zinc ascorbate under ambient conditions

Dalton Transactions ◽

10.1039/d0dt01329c ◽

2020 ◽

Vol 49 (23) ◽

pp. 7673-7679

Author(s):

Feda'a M. Al-Qaisi ◽

Abdussalam K. Qaroush ◽

Amneh H. Smadi ◽

Fatima Alsoubani ◽

Khaleel I. Assaf ◽

...

Keyword(s):

Mechanistic Study ◽

Ambient Conditions ◽

One Pot

A mechanistic study for efficient CO2 coupling with epoxides to yield the corresponding carbonates catalyzed by zinc ascorbate under ambient conditions under external additive-free conditions.

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Diastereoselective Synthesis of Spiro[Pyrrolo[2,1-B][1,3] Benzothiazole-3,5′-[1,3]Thiazolo[3,2-B][1,2,4]Triazol]-6′-Ones via Cycloaddition Reaction of Benzothiazolium Salts

Journal of Chemical Research ◽

10.3184/174751918x15314846558430 ◽

2018 ◽

Vol 42 (7) ◽

pp. 371-373 ◽

Cited By ~ 6

Author(s):

Qing Zeng ◽

Demin Ren ◽

Yulin Huang ◽

Xinliang Fu ◽

Xiaofang Li

Keyword(s):

Cycloaddition Reaction ◽

Crystallographic Analysis ◽

Azomethine Ylide ◽

Dipolar Cycloaddition ◽

Diastereoselective Synthesis ◽

X Ray

The 1,3-dipolar cycloaddition reaction of (Z)-5-arylidene[1,3]thiazolo[3,2-b][1,2,4]triazol-6(5H)-one and azomethine ylide, which was generated in situ by the reaction of N-4-methoxyphenacylbenzothiazolium bromides and triethylamine, afforded novel 2-(aryl)-1-(4-methoxybenzoyl)-1,2-dihydrospiro[pyrrolo[2,1-b][1,3]benzothiazole-3,5′-[1,3]thiazolo[3,2-b][1,2,4]triazol]-6′-ones in moderate yields. The structures of all the products were characterised thoroughly by NMR, IR and HRMS spectroscopy together with X-ray crystallographic analysis.

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

Organic & Biomolecular Chemistry ◽

10.1039/d1ob02042k ◽

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...

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

Organic & Biomolecular Chemistry ◽

10.1039/d1ob01135a ◽

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...

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