A Frustrated Lewis Pair Solution to a Frustrating Problem: Mono-Selective Functionalization of C–F Bonds in Di- and Trifluoromethyl Groups

Synlett ◽  
2020 ◽  
Vol 31 (10) ◽  
pp. 933-937
Author(s):  
Rowan D. Young ◽  
Richa Gupta ◽  
Amit K. Jaiswal ◽  
Dipendu Mandal
Keyword(s):  
Nucleophilic Substitution ◽  
Functional Groups ◽  
Bond Activation ◽  
Pyridinium Salts ◽  
Selective Functionalization ◽  
Frustrated Lewis Pair ◽  
Hydrogenation Reactions ◽  
Trifluoromethyl Groups

Polyfluoromethyl groups generally suffer from over-reaction, where multiple C–F bonds are uncontrollably functionalized. The use of a frustrated Lewis pair (FLP)-mediated C–F bond activation permits selective monodefluorination through base capture of intermediate fluorocarbocations. FLP-mediated C–F bond activation can be applied to aromatic, heteroaromatic, or nonaromatic difluoro and trifluoromethyl groups to generate selectively fluoride-substituted phosphonium and pyridinium salts. These salts can be further functionalized by Wittig coupling, nucleophilic substitution, photoredox alkylation, nucleophilic transfer, or hydrogenation reactions to install a range of functional groups into the activated C–F position.1 Introduction2 Frustrated Lewis Pair C–F Activation3 Conclusion

scholarly journals Metal-Free Borylation of Heteroarenes Using Ambiphilic Aminoboranes: On the Importance of Sterics in Frustrated Lewis Pair C–H Bond Activation

2017 ◽  
Vol 139 (41) ◽  
pp. 14714-14723 ◽  
Author(s):  
Julien Légaré Lavergne ◽  
Arumugam Jayaraman ◽  
Luis C. Misal Castro ◽  
Étienne Rochette ◽  
Frédéric-Georges Fontaine
Keyword(s):  
Bond Activation ◽  
Metal Free ◽  
Frustrated Lewis Pair

scholarly journals Development of variously functionalized nitrile oxides

2015 ◽  
Vol 11 ◽  
pp. 1241-1245 ◽  
Author(s):  
Haruyasu Asahara ◽  
Keita Arikiyo ◽  
Nagatoshi Nishiwaki
Keyword(s):  
Carboxylic Acid ◽  
Nucleophilic Substitution ◽  
Functional Groups ◽  
Grignard Reagent ◽  
Cycloaddition Reaction ◽  
Chemical Transformations ◽  
Nitrile Oxides ◽  
Weinreb Amide ◽  
Isoxazole Derivatives ◽  
Acid Esters

N-Methylated amides (N,4-dimethylbenzamide and N-methylcyclohexanecarboxamide) were systematically subjected to chemical transformations, namely, N-tosylation followed by nucleophilic substitution. The amide function was converted to the corresponding carboxylic acid, esters, amides, aldehyde, and ketone upon treatment with hydroxide, alkoxide, amine, diisobutylaluminium hydride and Grignard reagent, respectively. In these transformations, N-methyl-N-tosylcarboxamides behave like a Weinreb amide. Similarly, N-methyl-5-phenylisoxazole-3-carboxamide was converted into 3-functionalized isoxazole derivatives. Since the amide was prepared by the cycloaddition reaction of ethynylbenzene and N-methylcarbamoylnitrile oxide, the nitrile oxide served as the equivalent of the nitrile oxides bearing a variety of functional groups such as carboxy, alkoxycarbonyl, carbamoyl, acyl and formyl moieties.

ChemInform Abstract: Graphene Oxide Catalyzed C-H Bond Activation: The Importance of Oxygen Functional Groups for Biaryl Construction.

ChemInform ◽  
2016 ◽  
Vol 47 (26) ◽  
Author(s):  
Yongjun Gao ◽  
Pei Tang ◽  
Hu Zhou ◽  
Wei Zhang ◽  
Hanjun Yang ◽  
...  
Keyword(s):  
Graphene Oxide ◽  
Functional Groups ◽  
Bond Activation ◽  
Oxygen Functional Groups

scholarly journals Unsymmetrical Difunctionalization of Two Different C–H Bonds in One Pot Under Transition-Metal Catalysis

Synthesis ◽  
2018 ◽  
Vol 51 (01) ◽  
pp. 40-54 ◽  
Author(s):  
Masahito Murai ◽  
Kazuhiko Takai
Keyword(s):  
Transition Metal ◽  
Functional Groups ◽  
Aromatic Compounds ◽  
Transition Metal Catalysis ◽  
One Pot ◽  
Metal Catalysis ◽  
Selective Functionalization ◽  
Sequential Addition ◽  
Target Molecules ◽  
Directing Group

Recent advancements in unsymmetrical difunctionalization based on the substitution of two different C–H bonds in one-pot are described. Due to the difficulty of controlling reactivity and selectivity, multi-functionalization via substitution of several C–H bonds to install different functional groups has been limited until recently, in comparison with well-studied functionalization via sequential addition to unsaturated π-bonds. This difunctionalization protocol provides an efficient and rapid approach to a library of structurally complicated target molecules through the formation of multiple C–X bonds with high atom- and step-economy.1 Introduction2 ortho-Selective Functionalization of Two Different C–H Bonds Relative to the Directing Group2.1 Unsymmetrical Difunctionalization with the Introduction of Similar Functional Groups2.2 Unsymmetrical Difunctionalization with the Introduction of Different Functional Groups2.3 ortho-Selective Unsymmetrical Difunctionalization Promoted by Two Different Directing Groups Appearing During the Progress of the Reaction3 ortho/meta-Selective C–H Bond Difunctionalization Relative to the Directing Group4 Sequential Difunctionalization of Fused Aromatic Compounds and Heterocycles5 Summary and Outlook

scholarly journals Practical and Scalable Installation of Neglected S(VI) Functionality with Applications to the Enantiospecific Synthesis of Pharmaceuticals

2021 ◽  
Author(s):  
Zachary Shultz ◽  
Thomas Scattolin ◽  
Lukasz Wojtas ◽  
Justin Lopchuk
Keyword(s):  
Clinical Trials ◽  
Nucleophilic Substitution ◽  
Functional Groups ◽  
Modular Approach ◽  
New Wave ◽  
Pharmaceutical Applications ◽  
Enantiospecific Synthesis

<p>Sulfoximines and related sulfonimidoyl groups have been largely ignored for decades until their value was demonstrated in biological settings. The realization of their importance has ushered in a new wave of discovery and pharmaceutical applications. In attempts to remove the “neglected” description of the lesser-known S(VI) groups, a practical and modular approach for a-substituted heterocycles bearing sulfonimidoyl functional groups was developed. A variety of sulfoximines containing diverse functionality and complexity were rapidly introduced in an enantiospecific fashion with good to excellent yields. Pharmaceutically important heterocyclic scaffolds were shown to undergo the facile nucleophilic substitution, while sulfoximines, sulfonimidamides and sulfondiimines were all demonstrated to be compatible nucleophiles. The utility and practicality of the method was exhibited in target- and diversity-oriented syntheses of four sulfoximine-containing pharmaceuticals including ceralasertib, an ATR inhibitor currently in clinical trials. The introduction of underexplored sulfur functionality to common heterocyclic pharmacophores provides a practical platform for rapid analog development that is expected to aid future efforts in the discovery sciences.</p>

scholarly journals Reversible O–H bond activation by an intramolecular frustrated Lewis pair

2019 ◽  
Vol 48 (9) ◽  
pp. 2896-2899 ◽  
Author(s):  
Petra Vasko ◽  
M. Ángeles Fuentes ◽  
Jamie Hicks ◽  
Simon Aldridge
Keyword(s):  
Bond Activation ◽  
Frustrated Lewis Pairs ◽  
Frustrated Lewis Pair ◽  
Lewis Pairs

The interactions of the O–H bonds in alcohols, water and phenol with dimethylxanthene-derived frustrated Lewis pairs (FLPs) have been probed.

Using the Secondary PH/BH Functional Groups of an Active Geminal Frustrated Lewis Pair for Carbon Monoxide Reduction and Reactions with Nitriles and Isonitriles

2020 ◽  
Vol 132 (30) ◽  
pp. 12577-12583
Author(s):  
Jun Li ◽  
Christian Mück‐Lichtenfeld ◽  
Constantin G. Daniliuc ◽  
Gerald Kehr ◽  
Gerhard Erker
Keyword(s):  
Carbon Monoxide ◽  
Functional Groups ◽  
Frustrated Lewis Pair ◽  
Carbon Monoxide Reduction

scholarly journals Nickel-catalyzed C–N bond activation: activated primary amines as alkylating reagents in reductive cross-coupling

2019 ◽  
Vol 10 (16) ◽  
pp. 4430-4435 ◽  
Author(s):  
Huifeng Yue ◽  
Chen Zhu ◽  
Li Shen ◽  
Qiuyang Geng ◽  
Katharina J. Hock ◽  
...  
Keyword(s):  
Nickel Catalyst ◽  
Bond Activation ◽  
Cross Coupling ◽  
Aryl Halides ◽  
Primary Amines ◽  
Pyridinium Salts ◽  
Reaction Conditions ◽  
Alkyl Amines ◽  
Alkylating Reagents

The reductive cross coupling of pyridinium salts derived from readily available primary alkyl amines with aryl halides has been achieved under mild reaction conditions using a nickel catalyst.

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