Copper-Catalyzed Coupling of Acyl Chlorides with <i>gem</i>-Difluorinated Organozinc Reagents via Acyl Dithiocarbamates

Ashirbaev, Salavat S.; Levin, Vitalij V.; Стручкова, Марина И.; Dilman, Alexander D.

doi:10.1021/acs.joc.7b02598

Cited by 20 publications

(8 citation statements)

References 63 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This approach has been further extended to the synthesis of technologically important ternary and quaternary sul- Copper dithiocarbamates have not found widespread use in homogeneous catalysis, despite having many of the attributes associated with good catalysts such as a range of accessible oxidation states and coordinative unsaturation. While the reaction discussed above is formally catalytic, the amounts of copper used are near to stoichiometric; nevertheless, there soon followed a range of related transformations in which much smaller amounts of copper were utilised either in the presence of dithiocarbamates [313,314] or thiuram disulfides [315][316][317][318]. By way of example, Bolm and co-workers have reported that Cu 2 O is an efficient catalyst for the formation of aryl dithiocarbamates from the coupling of thiuram disulfides and aryl iodides [315].…”

Section: Discussionmentioning

confidence: 99%

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Hogarth

Onwudiwe

2021

Inorganics

View full text Add to dashboard Cite

Copper dithiocarbamate complexes have been known for ca. 120 years and find relevance in biology and medicine, especially as anticancer agents and applications in materials science as a single-source precursor (SSPs) to nanoscale copper sulfides. Dithiocarbamates support Cu(I), Cu(II) and Cu(III) and show a rich and diverse coordination chemistry. Homoleptic [Cu(S2CNR2)2] are most common, being known for hundreds of substituents. All contain a Cu(II) centre, being either monomeric (distorted square planar) or dimeric (distorted trigonal bipyramidal) in the solid state, the latter being held together by intermolecular C···S interactions. Their d9 electronic configuration renders them paramagnetic and thus readily detected by electron paramagnetic resonance (EPR) spectroscopy. Reaction with a range of oxidants affords d8 Cu(III) complexes, [Cu(S2CNR2)2][X], in which copper remains in a square-planar geometry, but Cu–S bonds shorten by ca. 0.1 Å. These show a wide range of different structural motifs in the solid-state, varying with changes in anion and dithiocarbamate substituents. Cu(I) complexes, [Cu(S2CNR2)2]−, are (briefly) accessible in an electrochemical cell, and the only stable example is recently reported [Cu(S2CNH2)2][NH4]·H2O. Others readily lose a dithiocarbamate and the d10 centres can either be trapped with other coordinating ligands, especially phosphines, or form clusters with tetrahedral [Cu(μ3-S2CNR2)]4 being most common. Over the past decade, a wide range of Cu(I) dithiocarbamate clusters have been prepared and structurally characterised with nuclearities of 3–28, especially exciting being those with interstitial hydride and/or acetylide co-ligands. A range of mixed-valence Cu(I)–Cu(II) and Cu(II)–Cu(III) complexes are known, many of which show novel physical properties, and one Cu(I)–Cu(II)–Cu(III) species has been reported. Copper dithiocarbamates have been widely used as SSPs to nanoscale copper sulfides, allowing control over the phase, particle size and morphology of nanomaterials, and thus giving access to materials with tuneable physical properties. The identification of copper in a range of neurological diseases and the use of disulfiram as a drug for over 50 years makes understanding of the biological formation and action of [Cu(S2CNEt2)2] especially important. Furthermore, the finding that it and related Cu(II) dithiocarbamates are active anticancer agents has pushed them to the fore in studies of metal-based biomedicines.

show abstract

Section: Discussionmentioning

confidence: 99%

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Hogarth

Onwudiwe

2021

Inorganics

View full text Add to dashboard Cite

show abstract

“…Existing methodologies for the construction of Ar–CF 2 –R linkages require reagents that are toxic, explosive, and of limited scope (Figure b) . The most common retrosynthetic disconnection is at the C–F bonds of the CF 2 unit through ketone deoxyfluorination using trifluorosulfuranes (e.g., DAST; Et 2 NSF 3 ) and radical fluorination of C–H bonds .…”

mentioning

confidence: 99%

The Difluoromethyl Group as a Masked Nucleophile: A Lewis Acid/Base Approach

2018

View full text Add to dashboard Cite

The difluoromethyl group (R-CFH) imparts desirable pharmacokinetic properties to drug molecules and is commonly targeted as a terminal functional group that is not amenable to further modification. Deprotonation of widely available Ar-CFH starting materials to expose nucleophilic Ar-CF synthons represents an unexplored, yet promising route to construct benzylic Ar-CF-R linkages. Here we show that the combination of a Brønsted superbase with a weak Lewis acid enables deprotonation of Ar-CFH groups and capture of reactive Ar-CF fragments. This route provides access to isolable and reactive Ar-CF synthons that react with a broad array of electrophiles at room temperature. The methodology is highly general in both electrophile and difluoromethyl (hetero)arene and can be applied directly to the synthesis of benzylic difluoromethylene (Ar-CF-R) linkages, which are useful lipophilic and metabolically resistant replacements for benzylic linkages in medicinal chemistry.

show abstract

“…Meanwhile, the group of Dilman [184] developed a method for the synthesis of difluorinated ketones with gem -difluorinated organozinc reagents (Scheme 110). Firstly, acyl chlorides reacted with potassium dithiocarbamate to generate S -acyl dithiocarbamates.…”

Section: Reviewmentioning

confidence: 99%

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

Shi

et al. 2019

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

Fluorine chemistry plays an increasingly important role in pharmaceutical, agricultural, and materials industries. The incorporation of fluorine-containing groups into organic molecules can improve their chemical and physical properties, which attracts continuous interest in organic synthesis. Among various reported methods, transition-metal-catalyzed fluorination/fluoroalkylation has emerged as a powerful method for the construction of these compounds. This review attempts to describe the major advances in the transition-metal-catalyzed incorporation of fluorine, trifluoromethyl, difluoromethyl, trifluoromethylthio, and trifluoromethoxy groups reported between 2011 and 2019.

show abstract

Copper-Catalyzed Coupling of Acyl Chlorides with gem-Difluorinated Organozinc Reagents via Acyl Dithiocarbamates

Cited by 20 publications

References 63 publications

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

The Difluoromethyl Group as a Masked Nucleophile: A Lewis Acid/Base Approach

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

Contact Info

Product

Resources

About