Microwave-assisted synthesis of substituted fluorophenyl mono- and diazides by SNAr. A fast methodology to prepare photoaffinity labeling and crosslinking reagents

Leyva, Elisa; Leyva, Socorro; González-Balderas, Regina M.; Loera, Denisse de

doi:10.1016/j.jfluchem.2013.10.002

Cited by 15 publications

(12 citation statements)

References 41 publications

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“…Fifthly, although the present methods for S N Ar of polyfluoroarenes are efficient in most cases, the combined use of other technologies such as microwave chemistry or flow-reaction systems may be conducive to further improve the reaction efficiency, e.g., reducing reaction time, elevating the reaction conversion rate, and allowing large-scale production. [30,33] Additionally, visible-light photoredox catalysis has recently emerged as an efficient and sustainable tool for organic transformations, which offers a unique way to harvest solar energy. [61] Generally, a single-electron transfer (SET) process between the photocatalysts and organic substrates is involved.…”

Section: Discussionmentioning

confidence: 99%

“…Thus, in‐depth theoretical and experimental studies are strongly called for to give accurate explanations of the reaction pathways, which are also helpful for designing new reactions and synthesizing novel molecules. Fifthly, although the present methods for S N Ar of polyfluoroarenes are efficient in most cases, the combined use of other technologies such as microwave chemistry or flow‐reaction systems may be conducive to further improve the reaction efficiency, e.g., reducing reaction time, elevating the reaction conversion rate, and allowing large‐scale production …”

Section: Discussionmentioning

confidence: 99%

“…The Leyva group reported a simple synthesis of substituted fluorophenyl mono-and diazides with the assistance of microwave irradiation (Scheme 26). [33] Scheme 24. Compared with the conventional routes, this method featured a rapid reaction rate and high product yield.…”

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

“…Aryl azides are high‐energy molecules that have been found to possess many applications in polymer chemistry and organic chemistry. The Leyva group reported a simple synthesis of substituted fluorophenyl mono‐ and diazides with the assistance of microwave irradiation (Scheme ) . Compared with the conventional routes, this method featured a rapid reaction rate and high product yield.…”

Section: Recent Achievements In the Transition‐metal‐free Snar Of Polmentioning

confidence: 99%

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Facile Access to Fluoroaromatic Molecules by Transition-Metal-Free C-F Bond Cleavage of Polyfluoroarenes: An Efficient, Green, and Sustainable Protocol

Liu

Zhang

2016

The Chemical Record

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The creation of new bonds via C-F bond cleavage of polyfluoroarenes has proven to be an important and powerful tool in synthetic chemistry. Using such a strategy, a myriad of valuable partially fluoroaromatic molecules and building blocks can be obtained. The transition-metal-free nucleophilic aromatic substitution (SN Ar) strategy has aroused the continuing interest of researchers due to its simple, mild, economical, and environmentally benign characteristics, which have been successfully applied to C-F bond functionalizations. In this account, we present a summary of the recent investigations of polyfluoroarenes involving SN Ar reactions and discuss some of our recent endeavors in the construction of partially fluoroaromatic molecules. Through this strategy, many new bonds including C-C, C-N, C-O, C-S, and C-H bonds can be created. Additionally, brief discussions on the transformation mechanisms are also provided. Finally, we discuss the existing limitations of the SN Ar reactions of polyfluoroarenes as well as our perspective on the future development of this chemistry.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

Section: Recent Achievements In the Transition‐metal‐free Snar Of Polmentioning

confidence: 99%

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Facile Access to Fluoroaromatic Molecules by Transition-Metal-Free C-F Bond Cleavage of Polyfluoroarenes: An Efficient, Green, and Sustainable Protocol

Liu

Zhang

2016

The Chemical Record

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“…In search of milder conditions, an alternative preparation of para ‐substituted fluorophenyl azides by S N Ar under microwave irradiation mw was recently reported by us. [ 13 ] In the present investigation, this procedure is applied to the preparation of several nitro‐ and fluoro‐substituted aryl azides. The application of microwave irradiation mw as a source of energy for reactions as become a convenient technique for organic chemistry.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of nitrophenyl and fluorophenyl azides and diazides by S_NAr under phase‐transfer or microwave irradiation: Fast and mild methodologies to prepare photoaffinity labeling, crosslinking, and click chemistry reagents

Leyva

Aguilar

González-Balderas

et al. 2020

J of Physical Organic Chem

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Two fast and mild methodologies to prepare nitrophenyl and fluorophenyl azides are presented. These aryl azides are extensively used as crosslinking, photoaffinity labeling, and click chemistry reagents. Substituted aryl azides are prepared by performing a SNAr substitution on halogenated benzenes with a phase‐transfer catalyst (PTC) such as tetraethylammonium tetrafluoroborate (TEATFB), the reaction proceeds in several hours under rather mild temperatures (25°C to 70°C). Furthermore, aryl azides are also prepared within minutes under microwave irradiation at slightly higher temperatures (50°C to 70°C). These procedures could be applied in the preparation of other aryl azides. In the case of substituted pentafluoro benzene (pF), the type of products obtained in each reaction depends on the amount of sodium azide and the strength and position of electron‐withdrawing substituents (COH, COR, COOR, CN, NO2, or F). A discussion on the mechanisms and the products obtained in these SNAr reactions is presented.

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Facile Generation of Heterotelechelic Poly(2‐Oxazoline)s Towards Accelerated Exploration of Poly(2‐Oxazoline)‐Based Nanomedicine

Van Guyse,

Abbasi,

Toh

et al. 2024

Angewandte Chemie

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Controlling the end‐groups of biocompatible polymers is crucial for enabling polymer‐based therapeutics and nanomedicine. Typically, end‐group diversification is a challenging and time‐consuming endeavor, especially for polymers pre‐pared via ionic polymerization mechanisms with limited functional group tolerance. In this study, we present a facile end‐group diversification approach for poly(2‐oxazoline)s (POx), enabling quick and reliable production of hetero‐telechelic polymers to facilitate POxylation. The approach relies on the careful tuning of reaction parameters to establish differential reactivity of a pentafluorobenzyl initiator fragment and the living oxazolinium chain‐end, allowing the selective introduction of N‐, S‐, O‐nucleophiles via the termination of the polymerization, and a consecutive nucleophilic para‐fluoro substitution. The value of this approach for the accelerated development of nanomedicine is demonstrated through the synthesis of well‐defined lipid‐polymer conjugates and POx‐polypeptide block‐copolymers, which are well‐suited for drug and gene delivery. Furthermore, we investigated the application of a lipid‐POx conjugate for the formulation and delivery of mRNA‐loaded lipid nanoparticles for immunization against the SARS‐COV‐2 virus, underscoring the value of POx as a biocompatible polymer platform.

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Microwave-assisted synthesis of substituted fluorophenyl mono- and diazides by SNAr. A fast methodology to prepare photoaffinity labeling and crosslinking reagents

Cited by 15 publications

References 41 publications

Facile Access to Fluoroaromatic Molecules by Transition-Metal-Free C-F Bond Cleavage of Polyfluoroarenes: An Efficient, Green, and Sustainable Protocol

Facile Access to Fluoroaromatic Molecules by Transition-Metal-Free C-F Bond Cleavage of Polyfluoroarenes: An Efficient, Green, and Sustainable Protocol

Synthesis of nitrophenyl and fluorophenyl azides and diazides by S_NAr under phase‐transfer or microwave irradiation: Fast and mild methodologies to prepare photoaffinity labeling, crosslinking, and click chemistry reagents

Facile Generation of Heterotelechelic Poly(2‐Oxazoline)s Towards Accelerated Exploration of Poly(2‐Oxazoline)‐Based Nanomedicine

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Microwave-assisted synthesis of substituted fluorophenyl mono- and diazides by SNAr. A fast methodology to prepare photoaffinity labeling and crosslinking reagents

Cited by 15 publications

References 41 publications

Facile Access to Fluoroaromatic Molecules by Transition-Metal-Free C-F Bond Cleavage of Polyfluoroarenes: An Efficient, Green, and Sustainable Protocol

Facile Access to Fluoroaromatic Molecules by Transition-Metal-Free C-F Bond Cleavage of Polyfluoroarenes: An Efficient, Green, and Sustainable Protocol

Synthesis of nitrophenyl and fluorophenyl azides and diazides by SNAr under phase‐transfer or microwave irradiation: Fast and mild methodologies to prepare photoaffinity labeling, crosslinking, and click chemistry reagents

Facile Generation of Heterotelechelic Poly(2‐Oxazoline)s Towards Accelerated Exploration of Poly(2‐Oxazoline)‐Based Nanomedicine

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Synthesis of nitrophenyl and fluorophenyl azides and diazides by S_NAr under phase‐transfer or microwave irradiation: Fast and mild methodologies to prepare photoaffinity labeling, crosslinking, and click chemistry reagents