Ni–Catalyzed Difunctionalization of Alkynyl Bromides with Thiosulfonates and N-Arylthio Succinimides: A Convenient Synthesis of 1,2-Thiosulfonylethenes and 1,1-Dithioethenes

Synthesis ◽  
2021 ◽  
Author(s):  
Raju Jannapu Reddy ◽  
Haritha Kumari Arram ◽  
Jagadesh Kumar Jangam ◽  
Rama Krishna Gamidi
Keyword(s):  
Scale Up ◽  
Radical Addition ◽  
Cesium Carbonate ◽  
One Pot ◽  
Convenient Synthesis ◽  
Wide Range ◽  
Atom Transfer Radical Addition ◽  
Plausible Mechanism ◽  
High Yields ◽  
And Control

An efficient Ni-catalyzed vicinal thiosulfonylation of 1-bromoalkynes with thiosulfonates in the presence of cesium carbonate has been described. An operationally simple and highly regioselective atom transfer radical addition (ATRA) of alkynyl bromides provided a wide range of (E)-1,2-thiosulfonylethenes (alpha-aryl-beta-thioarylvinyl sulfones) in moderate to high yields. The immense substrate scope of both alkynyl bromides and thiosulfonates were explored with a broad range of functional groups. Also, the indole derived 1,1-bromoalkenes were also successfully sightseen in 1,2-thiosulfonylation process. Moreover, the Ni-catalyzed geminal-dithiolation of alkynyl bromides with N-arylthio succinimides, thus providing 1,1-dithioalkenes in high yields. The present protocol is reliable at gram-scale, and a sequential one-pot bromination and thiosulfonylation of phenylacetylene have also been achieved in scale-up synthesis. A plausible mechanism is proposed to rationalize the experimental outcome and control experiments for the vicinal thiosulfonylation.

scholarly journals Cyclopropanation of Terminal Alkenes via Sequential Atom Transfer Radical Addition – 1,3-Elimination

2019 ◽  
Author(s):  
Nicholas D. C. Tappin ◽  
Weronika Michalska ◽  
Simon Rohrbach ◽  
Philippe Renaud
Keyword(s):  
Ethyl Acetate ◽  
Radical Addition ◽  
Atom Transfer ◽  
Reaction Sequence ◽  
One Pot ◽  
Tetrabutylammonium Fluoride ◽  
Wide Range ◽  
Atom Transfer Radical Addition ◽  
Simple Protocol ◽  
Terminal Alkenes

An operationally simple protocol to affect an atom transfer radical addition (ATRA) of commercially available ICH<sub>2</sub>Bpin to terminal alkenes has been developed. The intermediate iodide can be transformed in a one-pot process into the corresponding cyclopropane upon treatment with tetrabutylammonium fluoride (TBAF). This method is highly selective for the cyclopropanation of unactivated terminal alkenes over non-terminal alkenes and electron deficient alkenes. Due to the mildness of the procedure, a wide range of functional groups such as esters, amides, alcohols, ketones, and vinylic cyclopropanes are well tolerated. The whole reaction sequence relies on simple reagents such dilauroyl peroxide (DLP) and TBAF and can be run on multi-gram scales in ethyl acetate as a solvent.

Cyclopropanation of Terminal Alkenes via Sequential Atom Transfer Radical Addition – 1,3-Elimination

2019 ◽  
Author(s):  
Nicholas D. C. Tappin ◽  
Weronika Michalska ◽  
Simon Rohrbach ◽  
Philippe Renaud
Keyword(s):  
Ethyl Acetate ◽  
Radical Addition ◽  
Atom Transfer ◽  
Reaction Sequence ◽  
One Pot ◽  
Tetrabutylammonium Fluoride ◽  
Wide Range ◽  
Atom Transfer Radical Addition ◽  
Simple Protocol ◽  
Terminal Alkenes

An operationally simple protocol to affect an atom transfer radical addition (ATRA) of commercially available ICH<sub>2</sub>Bpin to terminal alkenes has been developed. The intermediate iodide can be transformed in a one-pot process into the corresponding cyclopropane upon treatment with tetrabutylammonium fluoride (TBAF). This method is highly selective for the cyclopropanation of unactivated terminal alkenes over non-terminal alkenes and electron deficient alkenes. Due to the mildness of the procedure, a wide range of functional groups such as esters, amides, alcohols, ketones, and vinylic cyclopropanes are well tolerated. The whole reaction sequence relies on simple reagents such dilauroyl peroxide (DLP) and TBAF and can be run on multi-gram scales in ethyl acetate as a solvent.

UV-Light-Induced Dehydrogenative N-Acylation of Amines with 2-Nitrobenzaldehydes to Give 2-Aminobenzamides

Synthesis ◽  
2022 ◽  
Author(s):  
Dishu Zeng ◽  
Tianbao Yang ◽  
Niu Tang ◽  
Wei Deng ◽  
Jiannan Xiang ◽  
...  
Keyword(s):  
Amino Acid ◽  
Organic Synthesis ◽  
Efficient Method ◽  
Building Block ◽  
Room Temperature ◽  
Uv Light ◽  
Amino Acid Derivatives ◽  
One Pot ◽  
Plausible Mechanism ◽  
High Yields

A simple, mild, green and efficient method for the synthesis of 2-aminobenzamides was highly desired in organic synthesis. Herein, we developed an efficient, one-pot strategy for the synthesis of 2-aminobenzamides with high yields irradiated by UV light. 32 examples proceeded successfully by this photo-induced protocol. The yield reached up to 92%. The gram scale was also achieved easily. This building block could be applied in the preparation of quinazolinones derivatives. Amino acid derivatives could be employed smoothly at room temperature. Finally, a plausible mechanism was proposed.

Photoorganocatalytic Atom Transfer Radical Addition of Bromoacetonitrile to Aliphatic Olefins

Synthesis ◽  
2018 ◽  
Vol 50 (17) ◽  
pp. 3395-3401 ◽  
Author(s):  
Christoforos Kokotos ◽  
Errika Voutyritsa ◽  
Nikolaos Nikitas ◽  
Mary Apostolopoulou ◽  
Anna Gerogiannopoulou
Keyword(s):  
Radical Addition ◽  
Synthetic Method ◽  
Atom Transfer ◽  
Wide Range ◽  
Atom Transfer Radical Addition

A green and cheap protocol for the photocatalytic atom transfer radical addition (ATRA) of bromoacetonitrile to aliphatic alkenes is presented. The use of benzoin methyl ehter as the photocatalyst and irradiation using a household lightbulb leads to a highly useful synthetic method for the conversion of a wide range of substituted aliphatic olefins into the corresponding bromonitriles.

A Green Approach for the Synthesis of Novel 7,11-Dihydro-6H-chromeno[3,4-e]isoxazolo[5,4-b]pyridin-6-one Derivatives Using Acidic Ionic Liquid [C4mim][HSO4]

2016 ◽  
Vol 69 (9) ◽  
pp. 1049 ◽  
Author(s):  
Sudesh Kumari ◽  
M. Rajeswari ◽  
Jitender M. Khurana
Keyword(s):  
Ionic Liquid ◽  
Crystal Packing ◽  
Aromatic Aldehydes ◽  
Green Solvent ◽  
One Pot ◽  
X Ray ◽  
Acidic Ionic Liquid ◽  
Green Approach ◽  
Wide Range ◽  
High Yields

A multicomponent reaction capable of affording a wide range of novel 7,11-dihydro-6H-chromeno[3,4-e]isoxazolo[5,4-b]pyridin-6-one derivatives via one-pot three-component condensation of 4-hydroxycoumarin, aromatic aldehydes, and 5-amino-3-methylisoxazole in ionic liquid 1-butyl-3-methylimidazolium hydrogen sulfate ([C4mim][HSO4]) is reported. Structures have been confirmed by spectral and X-ray studies. Crystal packing of 4b has also been reported. Green solvent, short reaction time, easy workup, and high yields are the salient features of the present protocol.

Additive- and Oxidant-Free Expedient Synthesis of Benzimidazoles Catalyzed by Cobalt Nanocomposites on N-Doped Carbon

Synlett ◽  
2019 ◽  
Vol 30 (03) ◽  
pp. 319-324 ◽  
Author(s):  
Zhaozhan Wang ◽  
Tao Song ◽  
Yong Yang
Keyword(s):  
Functional Group ◽  
Direct Synthesis ◽  
Biologically Active ◽  
One Pot ◽  
Mild Conditions ◽  
Wide Range ◽  
High Yields

A one-pot direct synthesis of a wide range of biologically active benzimidazoles through coupling of phenylenediamines and aldehydes catalyzed by a highly recyclable nonnoble cobalt nanocomposite was developed. A broad set of benzimidazoles can be efficiently synthesized in high yields and with good functional-group tolerance under additive- and oxidant-free mild conditions. The catalyst can be easily recycled for successive uses, and the process permits gram-scale syntheses of benzimidazoles.

The Discovery of Ultrasound Irradiation as a Useful Tool for Accelerating Petasis Three-component Reaction: Synthesis of α-Arylglycines

2018 ◽  
Vol 15 (2) ◽  
pp. 256-266 ◽  
Author(s):  
Fan Yun ◽  
Chunhui Cheng ◽  
Jingxuan Li ◽  
Pingwah Tang ◽  
Qipeng Yuan
Keyword(s):  
Reaction Time ◽  
Glyoxylic Acid ◽  
Reaction Times ◽  
Ultrasound Irradiation ◽  
Secondary Amines ◽  
One Pot ◽  
Petasis Reaction ◽  
Three Component Reaction ◽  
Wide Range ◽  
High Yields

Aim and Objective: α-Arylglycines belong to an important class of non-proteinogenic amino acids. Petasis 3-component, one-pot reaction lends itself to be suitable for the synthesis of α-Arylglycines. Because of the low reactivity, Petasis reaction requires long reaction time. Our objective is to use ultrasound irradiation to accelerate this versatile Petasis' synthesis of α-Arylglycines. Materials and Methods: Ultrasound irradiation as a physical tool to accelerate the Petasis 3-component reaction without any auxiliary catalyst can significantly shorten the reaction time. The operation is simple. It can be applied to a wide range of substrates. In order to highlight the remarkable utility of the ultrasound in Petasis reaction, we have compared side-by-side the reactivity between the reaction with ultrasound and the one without ultrasound. Results: Using ultrasound, the reaction times of Petasis reactions with various amine substrates including primary and secondary amines, heterocyclic amines, with a wide variety of boronic acids having different substituents (activating and deactivating groups) in the phenyl rings, and with glyoxylic acid and salicylic aldehyde were shortened from 5 to more than 20-fold. Conclusion: We have discovered the first examples of an efficient ultrasound-promoted approach for Petasis reaction to prepare a series of α-arylglycines in high yields and in excellent purities. The low reactivity of the reactions in this study were significantly enhanced by the ultrasound irradiation. By virtue of the acceleration and the operational simplicity, the present ultrasound assisted Petasis reaction can find applications in the synthetic areas of the already widely used Petasis three-component reaction.

DABCO as a green catalyst for the synthesis of pyranoquinoline derivatives

2017 ◽  
Vol 95 (5) ◽  
pp. 601-604 ◽  
Author(s):  
Ramin Ghorbani-Vaghei ◽  
Farid Rahmatpour ◽  
Narges Sarmast ◽  
Jafar Mahmoudi ◽  
Azadeh Shahriari
Keyword(s):  
One Pot ◽  
Green Catalyst ◽  
One Pot Synthesis ◽  
Convenient Synthesis ◽  
High Yields

In this study, a rapid and convenient synthesis of quinolines was developed. The reaction involves a one-pot synthesis of pyranoquinoline derivatives from aldehyde, malonitrile, and 8-hydroxyquinoline using DABCO as a catalyst at 80 °C in H2O/EtOH as the solvent in good to high yields.

2-Hydroxyethylammonium acetate as a reusable and cost-effective ionic liquid for the efficient synthesis of bis(pyrazolyl)methanes and 2-pyrazolyl-1-nitroalkanes

2012 ◽  
Vol 90 (10) ◽  
pp. 798-804 ◽  
Author(s):  
Sara Sobhani ◽  
Razieh Nasseri ◽  
Moones Honarmand
Keyword(s):  
Ionic Liquid ◽  
Michael Reaction ◽  
Scale Up ◽  
Reaction Times ◽  
Cost Effective ◽  
Environmentally Benign ◽  
One Pot ◽  
High Yields ◽  
Reaction Media ◽  
Task Specific Ionic Liquid

A new and convenient method for the synthesis of bis(pyrazolyl)methanes by one-pot tandem Knoevenagel–Michael reaction of 3-methyl-1-phenyl-5-pyrazolone with aryl, heteroaryl, or alkyl aldehydes in the presence of 2-hydroxyethylammonium acetate (2-HEAA) as a task-specific ionic liquid is described. This method was also successfully applied for the synthesis of 2-pyrazolyl-1-nitroalkanes by Michael addition of 3-methyl-1-phenyl-5-pyrazolone with β-nitrostyrenes in short reaction times. The present protocol offers several advantages such as using a reusable and cost-effective ionic liquid, an environmentally benign reaction media, being amenable to scale-up and good to high yields of the products.

scholarly journals Multicomponent Reactions, Solvent-Free Synthesis of 2-Amino-4-aryl-6-substituted Pyridine-3,5-dicarbonitrile Derivatives, and Corrosion Inhibitors Evaluation

2018 ◽  
Vol 2018 ◽  
pp. 1-9 ◽  
Author(s):  
Naglaa F. H. Mahmoud ◽  
Ahmed El-Sewedy
Keyword(s):  
Aromatic Aldehydes ◽  
Primary Amines ◽  
One Pot ◽  
Multicomponent Condensation ◽  
Wide Range ◽  
Elemental Analyses ◽  
High Yields ◽  
New Compounds ◽  
First Time ◽  
Solvent Free Synthesis

A number of 2-amino-4-aryl-6-substituted pyridine-3,5-dicarbonitrile derivatives were synthesized via one-pot multicomponent condensation reactions of different aromatic aldehydes with malononitrile and different primary amines, using different molecular ratios and different reaction conditions to achieve considerable product yields. Moreover, we succeed, for the first time to develop a new method to synthesize the aforementioned under the fusion condition without using solvent and catalysts. With this method, a wide range of novel 2-amino-3,5-dicyano-4-aryl-6-substituted aminopyridine derivatives were synthesized with high yields and board substrate of functional groups. The synthesized pyridine derivatives were found to have a corrosion inhibition efficiency, the rate of which increased with the increasing concentration of the derivatives. The structures of the new compounds were elucidated by spectroscopic data and elemental analyses.

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