Nonafluorobutanesulfonyl Azide as a Shelf-Stable Highly Reactive Oxidant for the Copper-Catalyzed Synthesis of 1,3-Diynes from Terminal Alkynes

Suárez, J. L.; Collado‐Sanz, Daniel; Cárdenas, Diego J.; Chiara, José Luis

doi:10.1021/jo5025909

Cited by 24 publications

(11 citation statements)

References 82 publications

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“…Therefore, direct metal‐catalyzed cross‐coupling of two terminal alkynes represents an attractive alternative; however, low selectivity towards the formation of the desired unsymmetrical diyne will typically yield significant amounts of the corresponding homocoupled diynes as side products. Optimization was achieved by using one alkyne in large excess, for example, 4‐ to 6‐fold in Cu‐, Ni/Cu‐ and Fe/Cu‐catalyzed reactions. Recently, several protocols were established that display larger heteroselectivity and provide sufficient yields of the unsymmetrical diyne with application of the major alkyne in only two‐fold or even lower excess .…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Mechanism of 1,3‐Diyne Cross‐Metathesis Catalyzed by Silanolate‐Supported Tungsten Alkylidyne Complexes

Schnabel

Melcher

Brandhorst

et al. 2018

Chemistry A European J

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The benzylidyne complex [PhC≡W{OSi(OtBu) } ] (1) catalyzed the cross-metathesis between 1,4-bis(trimethylsilyl)-1,3-butadiyne (2) and symmetrical 1,3-diynes (3) efficiently, which gave access to TMS-capped 1,3-diynes RC≡C-C≡CSiMe (4). Diyne cross-metathesis (DYCM) studies with C-labeled diyne PhC≡ C- C≡CPh (3*) revealed that this reaction proceeds through reversible carbon-carbon triple-bond cleavage and formation according to the conventional mechanism of alkyne metathesis. The reaction between 1 and 3* afforded the 3-phenylpropynylidyne complex PhC≡ C- C≡W{OSi(OtBu) } ] (5*), indicating that alkynylalkylidyne complexes are likely to act as catalytically active species. Attempts to isolate 5* from mixtures of 1 and 3* afforded crystals of the ditungsten 2-butyne-1,4-diylidyne complex [(tBuO) SiO} W≡ C- C≡ C- C≡W{OSi(OtBu) } ] (6*), which was additionally characterized by X-ray diffraction analysis. Depolymerization-macrocyclization of a carbazole-butadiyne polymer, obtained from 3,6-diethynyl-9-dodecylcarbazole (7) under copper-catalyzed Hay coupling conditions, was also efficiently catalyzed by 1 and afforded a mixture of mono-, diyne- and triyne-containing tetrameric macrocycles, revealing that diyne disproportionation into monoynes and triynes occurs as a slow side reaction that interferes with a high diyne metathesis selectivity. Potential catalytic pathways were studied by means of quantum-chemical calculations, and kinetic studies were performed to substantiate an α,α-mechanism for the catalytic diyne metathesis reaction, which involves intermediate alkynylalkylidyne and α,α'-dialkynylmetallacyclobutadiene intermediates.

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Section: Introductionmentioning

confidence: 99%

Unraveling the Mechanism of 1,3‐Diyne Cross‐Metathesis Catalyzed by Silanolate‐Supported Tungsten Alkylidyne Complexes

Schnabel

Melcher

Brandhorst

et al. 2018

Chemistry A European J

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“…The Yoshida correlation correctly flags all diazo transfer reagents, which are reported to be impact-sensitive with the exception of naphthalene-2-sulfonyl azide 21 . The more conservative Pfizer-modified correlation on the other hand flags NfN 3 and ADT, both of which have been experimentally demonstrated to be insensitive to impact. , para -Carboxybenzenesulfonyl azide ( p -CBSA) and p -ABSA are predicted to be insensitive to impact; however, there are reports of some impact sensitivity and they are categorized as “less sensitive” and infrequently react to impact loadings of almost 30 J. , …”

Section: Resultsmentioning

confidence: 99%

“…Both TsN 3 and MsN 3 have been prepared and used in flow, where the sulfonyl azide is maintained in a solution throughout the protocol and thus the explosive properties of the neat material are avoided . Among the more reactive diazo transfer reagents, NfN 3 , 2-azido-1,3-dimethylimidazolinium hexafluorophosphate (ADMP), and 25 have been demonstrated to be insensitive alternatives to the explosive TfN 3 . Friction and ESD sensitivity data are available for the imidazole-1-sulfonyl azide salts 24 – 29 and NfN 3 …”

Section: Introductionmentioning

confidence: 99%

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Thermal Stability and Explosive Hazard Assessment of Diazo Compounds and Diazo Transfer Reagents

Green

Wheelhouse

Payne

et al. 2019

Org. Process Res. Dev.

230

218

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Despite their wide use in academia as metal-carbene precursors, diazo compounds are often avoided in industry owing to concerns over their instability, exothermic decomposition, and potential explosive behavior. The stability of sulfonyl azides and other diazo transfer reagents is relatively well understood, but there is little reliable data available for diazo compounds. This work first collates available sensitivity and thermal analysis data for diazo transfer reagents and diazo compounds to act as an accessible reference resource. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and accelerating rate calorimetry (ARC) data for the model donor/acceptor diazo compound ethyl (phenyl)diazoacetate are presented. We also present a rigorous DSC dataset with 43 other diazo compounds, enabling direct comparison to other energetic materials to provide a clear reference work to the academic and industrial chemistry communities. Interestingly, there is a wide range of onset temperatures (T onset ) for this series of compounds, which varied between 75 and 160 °C. The thermal stability variation depends on the electronic effect of substituents and the amount of charge delocalization. A statistical model is demonstrated to predict the thermal stability of differently substituted phenyl diazoacetates. A maximum recommended process temperature (T D24 ) to avoid decomposition is estimated for selected diazo compounds. The average enthalpy of decomposition (ΔH D ) for diazo compounds without other energetic functional groups is −102 kJ mol −1 . Several diazo transfer reagents are analyzed using the same DSC protocol and found to have higher thermal stability, which is in general agreement with the reported values. For sulfonyl azide reagents, an average ΔH D of −201 kJ mol −1 is observed. High-quality thermal data from ARC experiments shows the initiation of decomposition for ethyl (phenyl)diazoacetate to be 60 °C, compared to that of 100 °C for the common diazo transfer reagent p-acetamidobenzenesulfonyl azide (p-ABSA). The Yoshida correlation is applied to DSC data for each diazo compound to provide an indication of both their impact sensitivity (IS) and explosivity. As a neat substance, none of the diazo compounds tested are predicted to be explosive, but many (particularly donor/acceptor diazo compounds) are predicted to be impact-sensitive. It is therefore recommended that manipulation, agitation, and other processing of neat diazo compounds are conducted with due care to avoid impacts, particularly in large quantities. The full dataset is presented to inform chemists of the nature and magnitude of hazards when using diazo compounds and diazo transfer reagents. Given the demonstrated potential for rapid heat generation and gas evolution, adequate temperature control and cautious addition of reagents that begin a reaction are strongly recommended when conducting reactions with diazo compounds.

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“…In this respect, many protocols have been developed, most of them usually require excess copper salt, the use of an unsafe poisonous ligand, excess oxidant, high reaction temperature or the presence of a co-catalyst. Some recent efforts report excellent improvement of this reaction by virtue of mild reaction conditions, a short time and base or a solvent-free reaction protocol (Fan et al, 2014;Cheng et al, 2014;Suá rez et al, 2015). Herein, we report a unique case of the pairwise accommodation of acyclic water trimer units in isolated cavities of the double stranded metal-organic assembly.…”

Section: Introductionmentioning

confidence: 97%

A double stranded metal–organic assembly accommodating a pair of water trimers in the host cavity and catalysing Glaser coupling

Pradhan

Moon

John

2016

Acta Crystallogr Sect B

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A supramolecular compound, catena-poly{[Cu2(1,3-μ2-(1a))2(μ2-ter)2(H2O)2]n·(6H2O)n} (1) has been synthesized using (1a) [(1a = N(1),N(3),N(5)-trimethyl-N(1),N(3),N(5)-tris((pyridin-4-yl)methyl)-1,3,5-benzene tricarboxamide] and terephthalate (ter) as the pillaring unit by self-assembly. The terephthalate units are connected by copper(II) ions forming a single strand, while a pair of such strands are then linked by (1a) via two pyridyl terminal arms bound to copper(II) nodes on either side forming a one-dimensional double stranded assembly propagating along the c axis. The compound crystallizes in the Fdd2 space group. The cavity created in the interior of this double strand assembly trap six water molecules and are stabilized by hydrogen bonding with the host. The arrangement of the pair of acyclic water trimers in isolated cavities of (1) is such that it resembles a closed-bracket-like formation. The Hirshfeld surface analysis of (1) reveals the presence of strong intermolecular hydrogen-bonding interactions between one-dimensional ladder-like units and with the water trimer in the host cavity. The copper(II)-containing coordination polymer also acts as an efficient catalyst for the Glaser-Hay homo-coupling reaction.

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Nonafluorobutanesulfonyl Azide as a Shelf-Stable Highly Reactive Oxidant for the Copper-Catalyzed Synthesis of 1,3-Diynes from Terminal Alkynes

Cited by 24 publications

References 82 publications

Unraveling the Mechanism of 1,3‐Diyne Cross‐Metathesis Catalyzed by Silanolate‐Supported Tungsten Alkylidyne Complexes

Unraveling the Mechanism of 1,3‐Diyne Cross‐Metathesis Catalyzed by Silanolate‐Supported Tungsten Alkylidyne Complexes

Thermal Stability and Explosive Hazard Assessment of Diazo Compounds and Diazo Transfer Reagents

A double stranded metal–organic assembly accommodating a pair of water trimers in the host cavity and catalysing Glaser coupling

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