Reaction of nitroalkanes with polyfluoroaromatic compounds

Vaidyanathaswamy, R.; Radha, K.; Dharani, M.; Raguraman, T.S.; Anand, Rajdeep

doi:10.1016/j.jfluchem.2012.09.004

Cited by 15 publications

(12 citation statements)

References 13 publications

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“…MP 67–71 °C (lit. 65–65.5 °C) 33 19 F NMR (376 MHz, Chloroform- d ) δ −87.80 (dq, J = 27.9, 13.1 Hz, 2F), −141.47 – −141.70 (m, 2F). 1 H NMR (400 MHz, Chloroform- d ) δ 5.70 (s, 2H).…”

Section: Methodsmentioning

confidence: 99%

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Selective and Scalable Perfluoroarylation of Nitroalkanes

Day

Weaver

2017

J. Org. Chem.

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Functionalized per- and poly-fluoroarenes are important building blocks, with many industrially and medicinally important molecules containing them. Nucleophilic aromatic substitution can be employed as a quick and straightforward way to synthesize these building blocks. While many methods to derivatize fluoroarenes exist which use heteroatom centered nucleophiles, there are fewer methods that use carbon centered nucleophiles, and of those many are poorly defined. This work presents the SNAr reaction of nucleophiles generated from nitroalkanes with a variety of fluorinated arenes. Given that the products are versatile, accessing polyfluorinated arene building blocks in substantial scale is important. This method is highly regioselective, and produces good to moderate yields on a large scale, sans chromatography, and thus fulfills this need. In addition, the regioselectivity of the addition was probed using both DFT calculations and experimentally via halogen exchange.

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Section: Methodsmentioning

confidence: 99%

“…m.p. 30–31 °C) 33 19 F NMR (376 MHz, Chloroform- d ) δ −137.85 – −138.07 (m, 2F), −139.64 – −139.84 (m, 2F). 1 H NMR (400 MHz, Chloroform-d) δ 5.58 (s, 2H), 3.95 (s, 3H).…”

Section: Methodsmentioning

confidence: 99%

Selective and Scalable Perfluoroarylation of Nitroalkanes

Day

Weaver

2017

J. Org. Chem.

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“…[49] Titanium trichloridei sc ommercially available as 20% solution in aqueous HCl and this reagent can be directly used for many applications.W ith acid-sensitive substrates NH 4 OAci sa dded to the reactionm ixture in order to provide ab uffering effect. [50] It should be observed that av ery large excesso ft he reactant (12 equiv.)…”

Section: R Eductive Methodsmentioning

confidence: 99%

The Nitro to Carbonyl Conversion (Nef Reaction): New Perspectives for a Classical Transformation

2015

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This review article reports new procedures and practical application of the nitro to carbonyl conversion that appeared in the literature after our\ud comprehensive report published in 2004. Beside traditional and well explored reactant systems, new procedures including the utilization of molecular oxygen and photoredox catalysis have been introduced for the Nef reaction. Of notable interest is the utilizationof the nitro to carbonyl conversion in tandem and cascade processes aimed at the preparation of hetero and carbocyclic derivatives

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“…The Vaidyanathaswamy group took advantage of the strong electron-withdrawing property of the nitro moiety and successfully realized the assembly of nitromethane and nitroethane with pentafluorobenzonitrile and methyl pentafluorobenzoate in the presence of DBU. [10] The C-F cleavage only occurred at the C4 position of the polyfluoroarenes, and C-F functionalization at other positions was not observed. Further transformations to other types of fluoroaromatic compounds demonstrated the versatile potential applications of the products (Scheme 3).…”

Section: C-c Bond-forming Reactionsmentioning

confidence: 98%

“…However, if a negative‐charge‐stabilizing group like nitro, carbonyl, or cyano is attached at the ortho position, the acidity of the α hydrogen may become enhanced, and the reaction of such unreactive bonds may become more feasible. The Vaidyanathaswamy group took advantage of the strong electron‐withdrawing property of the nitro moiety and successfully realized the assembly of nitromethane and nitroethane with pentafluorobenzonitrile and methyl pentafluorobenzoate in the presence of DBU . The C–F cleavage only occurred at the C4 position of the polyfluoroarenes, and C–F functionalization at other positions was not observed.…”

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

confidence: 99%

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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Reaction of nitroalkanes with polyfluoroaromatic compounds

Cited by 15 publications

References 13 publications

Selective and Scalable Perfluoroarylation of Nitroalkanes

Selective and Scalable Perfluoroarylation of Nitroalkanes

The Nitro to Carbonyl Conversion (Nef Reaction): New Perspectives for a Classical Transformation

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

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