Recent Advances in Halogen Bond-assisted Organic Synthesis

2020 ◽  
Vol 24 (18) ◽  
pp. 2118-2152
Author(s):  
Shigeyuki Yamada ◽  
Tsutomu Konno
Keyword(s):  
Organic Synthesis ◽  
Crystal Engineering ◽  
Electron Pair ◽  
Molecular Design ◽  
Halogen Bond ◽  
Covalent Bond ◽  
Lewis Base ◽  
Organic Transformations ◽  
Hydrogen Bond Interaction ◽  
Significant Attention

Halogen bond interactions, which take place between an electrophilic halogen and the electron-pair of a Lewis base and exhibit high directionality (approximately 180°), are non-covalent bond interactions similar to the hydrogen bond interaction. Many reports on halogen bond interactions have been published thus far, but many of them discuss halogen bond in the context of crystal engineering of supramolecular architecture. Since a seminal report by Bolm in 2008, halogen bond-assisted or -promoted organic synthesis has received significant attention. This review aims to introduce the molecular design of suitable halogen bond donors and organic transformations involving halogen bond interactions to afford a variety of organic compounds.

1,3,5-Tri(iodoethynyl)-2,4,6-trifluorobenzene: halogen-bonded frameworks and NMR spectroscopic analysis

2017 ◽  
Vol 73 (2) ◽  
pp. 153-162 ◽  
Author(s):  
Patrick M. J. Szell ◽  
Bulat Gabidullin ◽  
David L. Bryce
Keyword(s):  
Solid State ◽  
Crystal Engineering ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Lewis Base ◽  
Phosphonium Salts ◽  
Covalent Interaction ◽  
Framework Materials ◽  
Engineering Strategy ◽  
Triphenylphosphonium Bromide

Halogen bonding is the non-covalent interaction between the region of positive electrostatic potential associated with a covalently bonded halogen atom, named the σ-hole, and a Lewis base. Single-crystal X-ray diffraction structures are reported for a series of seven halogen-bonded cocrystals featuring 1,3,5-tris(iodoethynyl)-2,4,6-trifluorobenzene (1) as the halogen-bond donor, and bromide ions (as ammonium or phosphonium salts) as the halogen-bond acceptors: (1)·MePh3PBr, (1)·EtPh3PBr, (1)·acetonyl-Ph3PBr, (1)·Ph4PBr, (1)·[bis(4-fluorophenyl)methyl]triphenylphosphonium bromide, and two new polymorphs of (1)·Et3BuNBr. The cocrystals all feature moderately strong iodine–bromide halogen bonds. The crystal structure of pure [bis(4-fluorophenyl)methyl]triphenylphosphonium bromide is also reported. The results of a crystal engineering strategy of varying the size of the counter-cation are explored, and the features of the resulting framework materials are discussed. Given the potential utility of (1) in future crystal engineering applications, detailed NMR analyses (in solution and in the solid state) of this halogen-bond donor are also presented. In solution, complex13C and19F multiplets are explained by considering the delicate interplay between variousJcouplings and subtle isotope shifts. In the solid state, the formation of (1)·Et3BuNBr is shown through significant13C chemical shift changes relative to pure solid 1,3,5-tris(iodoethynyl)-2,4,6-trifluorobenzene.

The Synthesis and Application of Functionalized Mesoporous Silica SBA-15 as Heterogeneous Catalyst in Organic Synthesis

2020 ◽  
Vol 24 ◽  
Author(s):  
Ghodsi Mohammadi Ziarani ◽  
Shima Roshankar ◽  
Fatemeh Mohajer ◽  
Alireza Badiei
Keyword(s):  
Mesoporous Silica ◽  
Heterogeneous Catalyst ◽  
Organic Synthesis ◽  
Lewis Acid ◽  
Heterogeneous Catalysts ◽  
Organic Transformations ◽  
Functionalized Mesoporous Silica ◽  
Silica Nanomaterials ◽  
Wide Range ◽  
Target Molecules

Abstract:: Mesoporous silica nanomaterials provide an extraordinary advantage for making new and superior heterogeneous catalysts because of their surface silanol groups. The functionalized mesoporous SBA-15, such as acidic, basic, BrÖnsted, lewis acid, and chiral catalysts, are used for a wide range of organic synthesis. The importance of the chiral ligands, which were immobilized on the SBA-15, was mentioned in this review to achieve chiral products as valuable target molecules. Herein, their synthesis and application in different organic transformations are reviewed from 2016 till date 2020.

Recent Application of Polystyrene-supported Triphenylphosphine in Solid-Phase Organic Synthesis

2019 ◽  
Vol 23 (6) ◽  
pp. 643-678
Author(s):  
Lalthazuala Rokhum ◽  
Ghanashyam Bez
Keyword(s):  
Organic Synthesis ◽  
Combinatorial Chemistry ◽  
Solid Phase ◽  
Recent Application ◽  
Organic Transformations ◽  
Solid Phase Organic Synthesis ◽  
Wide Range ◽  
Fast Development ◽  
Polymer Supported

Recent years have witnessed a fast development of solid phase synthetic pathways, a variety of solid-supported reagent and its applications in diverse synthetic strategies and pharmaceutical applicability’s. Polymer-supported triphenylphosphine is getting a lot of applications owing to the speed and simplicity in the process. Furthermore, ease of recyclability and reuse of polymer-supported triphenylphosphine added its advantages. This review covers a wide range of useful organic transformations which are accomplished using cross-linked polystyrene-supported triphenylphosphine with the aim of giving renewed interest in the field of organic and medicinal-combinatorial chemistry.

Rhodamines as Photocatalyst in Organic Synthesis

2020 ◽  
Vol 07 ◽  
Author(s):  
Avik K. Bagdi ◽  
Papiya Sikdar
Keyword(s):  
Visible Light ◽  
Organic Synthesis ◽  
Organic Dyes ◽  
Transition Metal Catalysts ◽  
Visible Light Photocatalysis ◽  
Eosin Y ◽  
Organic Transformations ◽  
The Sustainable Development ◽  
Mechanistic Pathway ◽  
Green Model

Abstract:: Organic synthesis under environment friendly conditions has great impact in the sustainable development. In this context, visible light photocatalysis has emerged as a green model as this offers an energy-efficient pathway towards the organic transformation. Different transition-metal catalysts (Ir-, Ru-, Cu- etc) and organic dyes (eosin Y, rose bengal, methylene blue etc) are well-known photocatalysts in organic synthesis. Apart from the well-known organophotoredox catalysts, rhodamines (Rhodamine B and Rhodamine 6G) have been also employed as efficient photocatalysts for different organic transformations. In this review, we will focus on the photocatalysis by rhodamines in organic synthesis. Mechanistic pathway of the methodologies will also be discussed. We believe this review will stimulate the employment of rhodamines in the visible light photocatalysis for efficient organic transformations in the future.

scholarly journals Engineering the Interface between Inorganic Nanoparticles and Biological Systems through Ligand Design

Nanomaterials ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 1001
Author(s):  
Rui Huang ◽  
David C. Luther ◽  
Xianzhi Zhang ◽  
Aarohi Gupta ◽  
Samantha A. Tufts ◽  
...  
Keyword(s):  
Organic Synthesis ◽  
Molecular Design ◽  
Biological Systems ◽  
Ligand Design ◽  
Inorganic Nanoparticles ◽  
Organic Ligands ◽  
Biological Applications ◽  
Wide Range ◽  
Insight Into

Nanoparticles (NPs) provide multipurpose platforms for a wide range of biological applications. These applications are enabled through molecular design of surface coverages, modulating NP interactions with biosystems. In this review, we highlight approaches to functionalize nanoparticles with ”small” organic ligands (Mw < 1000), providing insight into how organic synthesis can be used to engineer NPs for nanobiology and nanomedicine.

scholarly journals Dichlorodioxomolybdenum(VI) Complexes: Useful and Readily Available Catalysts in Organic Synthesis

Synthesis ◽  
2018 ◽  
Vol 50 (20) ◽  
pp. 4019-4036 ◽  
Author(s):  
Roberto Sanz ◽  
Raquel Hernández-Ruiz
Keyword(s):  
Transition Metal Complexes ◽  
Lewis Acid ◽  
Short Review ◽  
Lewis Base ◽  
Phosphorus Compounds ◽  
Oxidation Reactions ◽  
Organic Transformations ◽  
Reduction Reactions ◽  
Acid Type ◽  
Catalyzed Reactions

Molybdenum(VI) dichloride dioxide (MoO2Cl2), and its addition complexes [MoO2Cl2(L)n; L = neutral ligand], are commercially or easily available and inexpensive transition-metal complexes based on a non-noble metal that can be applied as catalysts for various organic transformations. This short review aims to present the most significant breakthroughs in this field.1 Introduction2 Preparation and Reactivity of MoO2Cl2(L)n Complexes2.1 Synthesis and Structure2.2 Reactivity of Dichlorodioxomolybdenum(VI) Complexes3 Redox Processes Catalyzed by MoO2Cl2(L)n Complexes3.1 Deoxygenation Reactions Using Phosphorus Compounds3.2 Deoxygenation and Hydrosilylation Reactions Using Silanes3.3 Reduction Reactions Using Hydrogen3.4 Deoxygenation Reactions with Boranes and Thiols3.5 Reduction Reactions with Glycols3.6 Oxidation Reactions4 Ambiphilic Reactivity of MoO2Cl2 4.1 Amphoteric Lewis Acid–Lewis Base Catalyzed Reactions4.2 Lewis Acid Type Catalyzed Reactions5 Conclusion and Perspective

The aryl iodine-catalyzed organic transformation via hypervalent iodine species generated in situ

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Xuemin Li ◽  
Guangchen Li ◽  
Yifu Cheng ◽  
Yunfei Du
Keyword(s):  
Organic Synthesis ◽  
Oxidative Coupling ◽  
Hypervalent Iodine ◽  
Organic Transformations ◽  
Aryl Iodide ◽  
Oxidative Reaction ◽  
Iodine Species ◽  
Iodine Chemistry

Abstract The application of hypervalent iodine species generated in situ in organic transformations has emerged as a useful and powerful tool in organic synthesis, allowing for the construction of a series of bond formats via oxidative coupling. Among these transformations, the catalytic aryl iodide can be oxidized to hypervalent iodine species, which then undergoes oxidative reaction with the substrates and the aryl iodine regenerated again once the first cyclic cycle of the reaction is completed. This review aims to systematically summarize and discuss the main progress in the application of in situ-generated hypervalent iodine species, providing references and highlights for synthetic chemists who might be interested in this field of hypervalent iodine chemistry.

The double and triple role of L-(+)-tartaric acid and dimethyl urea: A prevailing green approach in organic synthesis

2021 ◽  
Vol 25 ◽  
Author(s):  
Rashid Ali ◽  
Ajay Kumar Chinnam ◽  
Vikas R. Aswar
Keyword(s):  
Tartaric Acid ◽  
Organic Synthesis ◽  
Low Cost ◽  
Organic Transformations ◽  
Green Approach ◽  
Dimethyl Urea ◽  
Low Toxicity ◽  
The One ◽  
Near Future

: The deep eutectic mixtures (DESs), introduced as novel alternative to usual volatile organic solvents for organic transformations has attracted a tremendous attention of the research community because of their low cost, negligible vapour pressure, low toxicity, biodegradability, recyclability, insensitive towards moisture, and readily availability from bulk renewable resources. Although, the low melting mixture of dimethyl urea (DMU)/L-(+)-tartaric acid (TA) is still infancy yet much effective as it play double and triple roles such as solvent, catalyst and/or reagent in a same pot for many crucial organic transformations. These unique properties of DMU/TA mixture prompted us to provide a quick overview of where the field stands presently, and where it might be going in near future. To our best knowledge, no review dealing with the applications of a low melting mixture of DMU/TA appeared in the literature except the one published in 2017 describing only the chemistry of indole systems. Therefore, we intended to reveal the developments of this versatile low melting mixture in the modern organic synthesis since its first report in 2011 by Köenig’s team to till date. Hopefully, the present review article will be useful to the researcher working not only in the arena of synthetic organic chemistry but also to the scientists working in other branches of science and technology.

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