Synthetic Methods for the Generation and Preparative Application of Benzyne

2010 ◽  
Vol 63 (7) ◽  
pp. 987 ◽  
Author(s):  
Tsugio Kitamura
Keyword(s):  
Organic Synthesis ◽  
Recent Progress ◽  
Synthetic Methods ◽  
Fluoride Ion ◽  
Mild Conditions ◽  
Frequent Use

Many methods have been developed for generating benzyne. Convenient and reliable precursors extensively studied so far involve benzenediazonium-2-carboxylate and o-dihalobenzenes such as 1,2-bromofluorobenzene and 1,2-dibromobenzene. Recently, in addition to the above precursors, o-(trimethylsilyl)phenyl triflate has been put into frequent use for benzyne reactions, in which benzyne is efficiently generated under mild conditions using fluoride ion. Furthermore, o-(trimethylsilyl)phenyliodonium triflate has been developed as a more efficient benzyne precursor. This mini-review focusses on recent progress in benzyne chemistry from the viewpoint of organic synthesis. The methods for generating benzynes are classified by the conditions into four categories: basic conditions using strong bases, mild conditions using fluoride ion, thermolysis, and oxidation.

scholarly journals A Review on Green Synthesis and Biological Activities of Nitrogen and Oxygen Containing Heterocycles

2021 ◽  
Author(s):  
Susheel Gulati ◽  
Rajvir Singh ◽  
Suman Sangwan
Keyword(s):  
Analytical Chemistry ◽  
Green Chemistry ◽  
Organic Synthesis ◽  
Material Science ◽  
Biological Activities ◽  
Review Article ◽  
Synthetic Methods ◽  
Mild Conditions ◽  
Environmental Friendly ◽  
Benign Solvents

Heterocycles are unique precursors for the synthesis of various pharmaceuticals and agrochemicals particularly those possessing N- or O- moieties. The development of methods to prepare heterocycles is of great importance in synthesis of organic compounds, especially the heterocycles which can be found in natural products. The synthesis of nitrogen and oxygen containing heterocycles viz. coumarins, dihydropyrimidinones, imidazoles, isoxazoles and benzimidazoles represented an attractive and demanding work for chemists as these nucleus has found extensive applications in several fields such as material science, analytical chemistry and most importantly in medicinal chemistry. Organic synthesis has been attracted towards the development of new environmental friendly procedures to achieve the goals of green chemistry. The fundamental aspects of green chemistry are use of biocatalysts and environmental benign solvents under mild conditions. The present review article summarized the green synthetic methods and biological activities of nitrogen and oxygen containing heterocycles.

Recent Progress in Arylation Reactions with Diaryliodonium Salts

2021 ◽  
Vol 25 ◽  
Author(s):  
Dan Wang ◽  
Qian Li ◽  
Mengting Li ◽  
Zhengyin Du ◽  
Ying Fu
Keyword(s):  
Organic Synthesis ◽  
Recent Progress ◽  
Large Range ◽  
Bond Formation ◽  
Cascade Reactions ◽  
High Reactivity ◽  
Synthetic Methods ◽  
Research Progress ◽  
Diaryliodonium Salts

Abstract: In recent years, diaryliodonium salts have been extensively exploited as green, efficient electrophilic arylation reagents in a large range of organic synthesis. These arylating reagents exhibit relatively high reactivity and good selectivity in many transformations. In this review, the synthetic methods towards diaryliodonium salts are described briefly. The research progress in arylation reactions by using diaryliodonium in C-C and carbon-heteroatom bond formation, especially in enantioselective C-C bond formation and cascade reactions, in past ten years is summarized and discussed in detail.

Double Ring-Closing Approach for the Synthesis of 2,3,6,7-Substituted Anthracene Derivatives

2020 ◽  
Author(s):  
Birgit Meindl ◽  
Katharina Pfennigbauer ◽  
Berthold Stöger ◽  
Martin Heeney ◽  
Florian Glöcklhofer
Keyword(s):  
Wittig Reaction ◽  
Condensation Reaction ◽  
Synthetic Methods ◽  
Anthracene Derivative ◽  
Double Ring ◽  
Mild Conditions ◽  
Wide Range ◽  
Anthracene Derivatives

Anthracene derivatives have been used for a wide range of applications and many different synthetic methods for their preparation have been developed. However, despite continued synthetic efforts, introducing substituents in some positions has remained difficult. Here we present a method for the synthesis of 2,3,6,7-substituted anthracene derivatives, one of the most challenging anthracene substitution patterns to obtain. The method is exemplified by the preparation of 2,3,6,7-anthracenetetracarbonitrile and employs a newly developed, stable protected 1,2,4,5-benzenetetracarbaldehyde as the precursor. The precursor can be obtained in two scalable synthetic steps from 2,5-dibromoterephthalaldehyde and is converted into the anthracene derivative by a double intermolecular Wittig reaction under very mild conditions followed by a deprotection and intramolecular double ring-closing condensation reaction. Further modification of the precursor is expected to enable the introduction of additional substituents in other positions and may even enable the synthesis of fully substituted anthracene derivatives by the presented approach.<br>

O-AcylTEMPOs, a Modified and Fundamental, but Unexplored Carboxylic Derivative: Recent Progress in Synthetic Applications

2019 ◽  
Vol 23 (19) ◽  
pp. 2102-2121
Author(s):  
Hiroyuki Kawafuchi ◽  
Lijian Ma ◽  
Md Imran Hossain ◽  
Tsutomu Inokuchi
Keyword(s):  
Organic Synthesis ◽  
Recent Progress ◽  
Knoevenagel Condensation ◽  
Acid Synthesis ◽  
Amino Acid Synthesis ◽  
Electrophilic Amination ◽  
Weinreb Amides ◽  
Anionic Species ◽  
Diastereoselective Addition ◽  
Carbonyl Function

O-Acylated 2,2,6,6-tetramethylpiperidine-N-oxyls (abbr. O-AcylTEMPOs) are easily available and stable carboxylic derivatives, but their utility in organic synthesis is unexplored in contrast to analogues, such as the N-methoxy-N-methylamides, known as Weinreb amides. Especially, the O–N unit of the O-acylTEMPOs dictates a fairly electronwithdrawing character for the carbonyl function. This enhances the reactivity and stability of the resulting enolate ions. Accordingly, O-acylTEMPOs allow various transformations and this review encompasses seven topics: (1) Reactivity of O-acylTEMPOs towards nucleophiles and chemoselective transformations, (2) Reactivity of anionic species derived from O-acylTEMPOs, (3) E-Selective Knoevenagel condensation of acetoacetylTEMPOs and synthesis of furans, (4) Electrocyclization of 2,4-dienones derived from acetoacetic derivatives and 2-substituted enals, (5) Diastereoselective addition of amide anion to O-(2-alkenoyl)TEMPOs and &#946;-amino acid synthesis, (6) Thermolysis of O-acylTEMPOs, and (7) Applications for Umpolung reactions using O-benzoylTEMPOs, useful for the electrophilic amination of alkenes and alkynes.

scholarly journals Photocatalytic three-component asymmetric sulfonylation via direct C(sp3)-H functionalization

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Shi Cao ◽  
Wei Hong ◽  
Ziqi Ye ◽  
Lei Gong
Keyword(s):  
Asymmetric Catalysis ◽  
Organic Synthesis ◽  
Photochemical Reaction ◽  
Low Cost ◽  
Bioactive Molecules ◽  
Atom Economy ◽  
Mild Conditions ◽  
Wide Range ◽  
Unsaturated Carbonyl Compound ◽  
Direct Functionalization

AbstractThe direct and selective C(sp3)-H functionalization of cycloalkanes and alkanes is a highly useful process in organic synthesis owing to the low-cost starting materials, the high step and atom economy. Its application to asymmetric catalysis, however, has been scarcely explored. Herein, we disclose our effort toward this goal by incorporation of dual asymmetric photocatalysis by a chiral nickel catalyst and a commercially available organophotocatalyst with a radical relay strategy through sulfur dioxide insertion. Such design leads to the development of three-component asymmetric sulfonylation involving direct functionalization of cycloalkanes, alkanes, toluene derivatives or ethers. The photochemical reaction of a C(sp3)-H precursor, a SO2 surrogate and a common α,β-unsaturated carbonyl compound proceeds smoothly under mild conditions, delivering a wide range of biologically interesting α-C chiral sulfones with high regio- and enantioselectivity (>50 examples, up to >50:1 rr and 95% ee). This method is applicable to late-stage functionalization of bioactive molecules, and provides an appealing access to enantioenriched compounds starting from the abundant hydrocarbon compounds.

scholarly journals Recent progress on the corrosion behavior of metallic materials in HF solution

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Hailong Dai ◽  
Shouwen Shi ◽  
Lin Yang ◽  
Can Guo ◽  
Xu Chen
Keyword(s):  
Environmental Factors ◽  
Stainless Steels ◽  
Hydrofluoric Acid ◽  
Recent Progress ◽  
Future Research ◽  
Fluoride Ion ◽  
Metallic Materials ◽  
Chemical Coupling ◽  
Corrosion Behaviors ◽  
Corrosion Mechanisms

Abstract Hydrofluoric acid (HF) or fluoride ion corrosion issues are often encountered in many fields, which have attracted extensive research due to its strong corrosiveness. In this paper, a critical review is presented based on recent progress on HF corrosion. In view of the discrepancy of fluoride ion compared with other ions, the special attack characteristics of fluoride ion are firstly discussed. Afterwards, the corrosion mechanisms of stainless steels, nickel-based alloys, and titanium alloys in HF solution or fluoride ion-containing environment are reviewed, and three typical corrosion behaviors are summarized, which are essentially weakening process of passivation of metallic materials. The effects of influencing factors (e.g. alloying elements, environmental factors, and stress, etc.) on HF corrosion are also discussed, which involve changes in passivation mechanism, the influence of HF attack mode and multiple damage mechanisms due to mechanical–chemical coupling. Finally, future research works on HF corrosion are proposed.

Sēra dioksīda fizikāli ķīmisko īpašību pielietojums jaunu organiskās sintēzes metožu izstrādē / Development of New Organic Synthesis Methods Based on Physico-Chemical Properties of Sulfur Dioxide

2021 ◽  
Author(s):  
◽  
Krista Gulbe
Keyword(s):  
Organic Synthesis ◽  
Chemical Properties ◽  
Coupling Reaction ◽  
Synthetic Methods ◽  
Synthesis Methods ◽  
Chemical Transformations ◽  
Scientific Publications ◽  
Cross Coupling Reaction ◽  
Aryl Acetylenes ◽  
The Republic

The Doctoral Thesis has been prepared as a collection of thematically related scientific publications comprising five publications in the SCI journals, one patent of the Republic of Latvia, and one application for patent of the Republic of Latvia. We have carried out fundamental research on the applications of SO2 as a solvent and reagent in organic synthesis. We have developed several novel synthetic methods that represent the use of liquid SO2 as a solvent for chemical transformations that proceed via carbenium ion intermediates: a) hydration of aryl acetylenes; b) hydrohalogenation of aryl acetylenes; c) ring opening of methylenecyclopropanes with halides; d) glycosylation with glycosyl fluorides. By employing DABSO as an SO2 surrogate, we have also discovered the catalytic activity of Ru(II) complexes towards sulfonylative cross coupling reaction. This finding has been applied for the synthesis of sulfonyl derived compounds.

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