Riconosciamo generosi fondi di start-up della State University di New York a Stony Brook, a sostegno di questo lavoro. Ringraziamo anche TOSOH F-Tech, Inc. per averci fornito TMSCF 3 reagenti per la sintesi di Togni reagente II.

1. Precursore Preparazione: Sintesi di metile 4- (N -hydroxyacetamido) benzoato (1a) <ol><li> Riduzione di metil 4-nitrobenzoato. <ol><li> Aggiungere 5,00 g di metil 4-nitrobenzoato (27,6 mmol, 1,00 equiv), 159 mg di 5% su carbone Rodio (Rh / C, 0.300 mol% Rh), e un fritto barra magnetica in un forno-essiccato 250 ml a due collo pallone a fondo tondo (essiccato a 150 ° C per 18 ore). NOTA: I reagenti possono essere pesati sotto atmosfera ambiente. Tuttavia, la reazione deve essere effettuata in atmosfera di azoto. </li><li> Collegare un collo del pallone di azoto / collettore del vuoto e tappare l&#39;altro collo con un setto. Eseguire tre cicli di vuoto-ricarica (cioè, il pompaggio di aria fuori del pallone e sostituendo il vuoto risultante con gas azoto) per sostituire l&#39;aria nel pallone con azoto. </li><li> Aggiungere 138 ml di tetraidrofurano anidro (THF, 0,200 M) al pallone di reazione mediante siringa ermetico. Fresco e mescolare le mixt reazioneure a 0 ° C per 15 min. </li><li> Aggiungere 1,47 ml di idrazina monoidrato (1,52 g, 30,4 mmol, 1,20 equiv) goccia a goccia alla miscela di reazione a 0 ° C utilizzando una siringa a tenuta d&#39;aria. Monitorare la reazione utilizzando una cromatografia su strato sottile (TLC). Utilizzare esano: acetato di etile (EtOAc) (4: 1 v / v, R f = 0,23) come eluente per sviluppare la TLC. </li><li> Quando metil 4-nitrobenzoato è completamente consumato, filtrare la miscela di reazione attraverso un breve pad di terra di diatomee (cioè, Celite, 5 g) in 60 ml di fritta imbuto Buchner con filtrazione sottovuoto. Lavare il filtro con EtOAc (20 ml x 3 volte). Concentrare il filtrato sotto vuoto usando un evaporatore rotante per permettere il benzoato di metile grezzo 4- (N -hydroxyamino), che è usato direttamente senza ulteriore purificazione. </li></ol></li><li> Protezione acetil di metil 4- (N -hydroxyamino) benzoato <ol><li> Aggiungere 2,55 g di bicarbonato di sodio (NaHCO3, 30,4 mmol, 1,20 equiv), tutto il greggiometil 4- (N -hydroxyamino) benzoato ottenuto dal passaggio precedente, e un fritto bar in una da 500 ml a due colli pallone a fondo del forno-essiccato. </li><li> Cap un collo con un setto e collegare un altro collo di un collettore di azoto / vuoto. Eseguire tre cicli di vuoto-ricarica per sostituire l&#39;aria nel pallone con azoto. </li><li> Aggiungere 138 ml di etere dietilico anidro (Et 2 O, 0,200 M) al pallone di reazione utilizzando una siringa a tenuta d&#39;aria. Raffreddare e agitare la miscela di reazione a 0 ° C per 15 min. </li><li> Preparare una soluzione di cloruro di acetile (2,17 ml, 2,39 g, 30,4 mmol, 1,20 equiv) in Et 2 O anidro (138 ml, 0,220 M). Aggiungere la soluzione alla miscela di reazione a 0 ° C utilizzando una pompa a siringa ad una velocità di 10,0 ml / h. </li><li> Al termine dell&#39;aggiunta, filtrare la miscela di reazione attraverso un breve pad di terra di diatomee (cioè, Celite, 5 g) in 60 ml di fritta imbuto Buchner con filtrazione sottovuoto. Lavare il filtro con EtOAc (20 ml x 3 volte). Concentrare ilfiltrato sotto vuoto usando un evaporatore rotante. </li><li> Purificare il prodotto grezzo con colonna cromatografia flash 35 eluendo con esano: EtOAc (4: 1 a 1: 1 (v / v)) (R f = 0,13, esano: EtOAc (4: 1 (v / v)) per ottenere 5,31 g di metil 4- (N -hydroxyacetamido) benzoato come un giallo solido (25,4 mmol, 92% di resa) luce. </li></ol></li></ol> 2. Sintesi di metil 4- (N - (trifluorometossi) acetammido) benzoato (2a) <ol><li> Aggiungere 2,00 g di metil 4- (N -hydroxyacetamido) benzoato (1a) (9,56 mmol, 1,00 equiv), 311 mg di Cs 2 CO 3 (0,956 mmol, 10,0 mol%), 3,63 g di Togni reagente II (11,5 mmol, 1.20 equiv), e un fritto barra magnetica in un 250 ml pallone da forno secchi all&#39;interno di un vano portaoggetti (atmosfera di azoto). NOTA: Questa reazione può essere effettuata anche mediante tecniche di Schlenk fuori del cassetto portaoggetti. Attenzione: Pure reagente Togni II è l&#39;impatto e l&#39;attrito sensibile, fiamme liberes, scintille, e / o rettifica dovrebbe essere evitato. Strumenti morbidi e levigati devono essere utilizzati per le manipolazioni. Inoltre, la miscela di reazione deve essere agitata dietro uno schermo di sicurezza. 36 </li><li> Aggiungere 95,6 ml di essiccato e degassato cloroformio (CHCl3, 0,100 M) al pallone di reazione. </li><li> Chiudere la beuta con setto e agitare la miscela di reazione a 23 ° C sotto atmosfera di N 2 all&#39;interno o all&#39;esterno del vano portaoggetti per 16 ore. </li><li> Filtrare la miscela di reazione attraverso un imbuto filtrante per rimuovere eventuali residui solidi. Concentrare il filtrato sotto vuoto usando un evaporatore rotante. </li><li> Purificare il prodotto grezzo con cromatografia flash eluendo con esano: diclorometano (CH 2 Cl 2) (7: 3 a 0: 1 (v / v)) (R f = 0,44 (CH 2 Cl 2) permettere 2,51 g di metil 4- (N - (trifluorometossi) acetammido) benzoato (9,05 mmol, 95% resa). NOTA: Togni reagente II è accordo preparatozione alle procedure letteratura 37 e memorizzati nel cassetto portaoggetti congelatore a -35 ° C per mantenere la sua qualità per un lungo periodo di tempo. Questa reazione è ossigeno sensibile. Sebbene tutti i reagenti possono essere pesati sotto atmosfera ambiente a temperatura ambiente, la rimozione di tutto l&#39;ossigeno dal pallone di reazione è critica. Essiccato e degassato CHCl3 viene preparato mediante distillazione da CaH 2 in atmosfera di azoto seguita eseguendo tre cicli di congelamento-procedura pompa-disgelo. </li></ol> 3. Sintesi di Metil-4 Acetamido-3- (trifluorometossi) benzoato via OCF 3 -migration (3a) <ol><li> Aggiungere 2,51 g metile 4- (N - (trifluorometossi) acetammido) benzoato (9.05 mmol, 1,0 equiv), un fritto barra magnetica, e 9,05 ml di Meno 2 (1,00 m) in un recipiente a pressione da 50 ml. Tappare il recipiente con un tappo a vite. </li><li> Mescolare la miscela di reazione a 120 ° C dietro lo schermo di protezione per 20 ore. Attenzione: nitrometano Impureè esplosivo, quindi la miscela di reazione deve essere agitata dietro lo schermo di protezione. </li><li> Raffreddare la miscela di reazione di RT. </li><li> Trasferire la miscela di reazione in un pallone a fondo rotondo da 100 ml. </li><li> Concentrare la miscela di reazione sotto vuoto usando un evaporatore rotante. </li><li> Purificare il prodotto grezzo con cromatografia flash eluendo con esano: EtOAc (9: 1 a 7: 3 (v / v)) (R f = 0,51 esano: EtOAc (4: 1 (v / v)) per ottenere 2,13 g di metil 4-acetamido-3- (trifluorometossi) benzoato (7,69 mmol, 85%). NOTA: Questa reazione può essere condotta in atmosfera ambiente. Atmosfera di azoto non è necessaria. Un pallone a fondo tondo dotato di un condensatore acqua può essere utilizzata come un apparato reazione alternativa. </li></ol> 4. Caratterizzazione di nuovi prodotti <ol><li> Caratterizzare tutti i nuovi composti da 1 H, 13 spettroscopia NMR C e spettroscopia di massa ad alta risoluzione e utilizzare 19 spettroscopia NMR Fper caratterizzare composti contenenti atomi di fluoro. 34 </li></ol>

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Dev. 17, 318-319 (2013).</li><li>Matousek, V., Pietrasiak, E., Schwenk, R., Togni, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=One-pot+synthesis+of+hypervalent+iodine+reagents+for+electrophilic+trifluoromethylation.">One-pot synthesis of hypervalent iodine reagents for electrophilic trifluoromethylation.</a> J. Org. Chem. 78, 6763-6768 (2013).</li></ol>

The authors declare no competing financial interests.

A causa della mancanza di una procedura generale e user-friendly per la sintesi di areni trifluoromethoxylated, molti OCF composti aromatici 3 -non sono estremamente costosi. 34 La nostra strategia sposta un&#39;ampia tolleranza gruppo funzionale e fornisce un facile accesso alle varie areni trifluoromethoxylated. Questi composti potrebbero servire come mattoni importanti per la scoperta e lo sviluppo di nuovi prodotti farmaceutici, prodotti agrochimici, e materiali. Id...

Il trifluorometossi (OCF 3) gruppo ha fatto un profondo impatto sulla ricerca di vita e la scienza dei materiali in quanto la prima sintesi di trifluoromethyl dell&#39;etere nel 1935. 2 Grazie alla sua combinazione unica di alta elettronegatività (χ = 3.7) 3 ed eccellente lipofilia (Π x = 1.04), 4 il gruppo trifluorometossi ha trovato ampie applicazioni in medicina, agricoltura, industria e materiali. 5-10 Tuttavia, l&#39;introduzione facile del gruppo OCF 3 in molecole organiche, in particolare i composti aromatici, rimane una sfida importante nella chimica di sintesi. Nel corso degli ultimi decenni, gli sforzi per affrontare questa sfida ha portato allo sviluppo di una manciata di trasformazioni per la sintesi di areni trifluoromethoxylated 5-7,9-11 Questi includono (i) scambio di cloro / fluoro sui precursori trichlorinated;. 1,12 -17 (ii) deoxyfluorination di fluoroformiati; 18 </sup&gt; (iii) fluorodesulfurization ossidativo; 19-21 (iv) trifluoromethylation elettrofila di alcoli, 22-25 (v) trifluoromethoxylation nucleofila, 26-30, (vi) di transizione trifluoromethoxylation metallo-mediata di borato arilici e stannani, 31 e (vii ) trifluoromethoxylation radicale. 32,33 Tuttavia, molti di questi approcci sia soffrono di applicazione substrato scarsa o richiede l&#39;uso di reagenti altamente tossici e / o termicamente labili. Pertanto, a causa della mancanza di un metodo generale e di facile utilizzo per sintetizzare OCF 3 composti -aventi tenore, il potenziale del gruppo OCF 3 non è stata completamente sfruttata in chimica. Come parte del nostro interesse per reazioni trifluoromethoxylation, 34 descriviamo qui un protocollo a due fasi (cioè, O -trifluoromethylation radicale e OCF indotta termicamente 3 -migration) per la sintesi di metil 4-acetamido-3- (trifluorometossi) benzoato (3a) da metil 4- (N -hydroxyacetamido) benzoato (1a). La strategia è facile da usare e applicabili alla sintesi di una vasta gamma di orto derivati ​​dell&#39;anilina -trifluoromethoxylated.

<table border="0" cellpadding="0" cellspacing="0" width="573">
	<tbody>
		<tr height="43">
			<td height="43" style="height:43px;width:216px;">5% Rhodium on carbon</td>
			<td style="width:71px;">Aspira Scientific</td>
			<td style="width:119px;">300835</td>
			<td style="width:167px;">5% wt% dry loading</td>
		</tr>
		<tr height="43">
			<td height="43" style="height:43px;width:216px;">hydrazine monohydrate</td>
			<td style="width:71px;">Sigma-Alderich</td>
			<td style="width:119px;">13696HMV</td>
			<td style="width:167px;">Reagent grade, 98%</td>
		</tr>
		<tr height="43">
			<td height="43" style="height:43px;width:216px;">Acetyl chloride</td>
			<td style="width:71px;">Alfa Aesar</td>
			<td style="width:119px;">10176887</td>
			<td style="width:167px;">98%</td>
		</tr>
		<tr height="43">
			<td height="43" style="height:43px;width:216px;">Sodium bicarbonate</td>
			<td style="width:71px;">Fisher Scientific</td>
			<td style="width:119px;">134826</td>
			<td style="width:167px;">Chemical pure</td>
		</tr>
		<tr height="43">
			<td height="43" style="height:43px;width:216px;">Cesium carbonate</td>
			<td style="width:71px;">Alfa Aesar</td>
			<td style="width:119px;">12887</td>
			<td style="width:167px;">99.9%, metals basis</td>
		</tr>
		<tr height="148">
			<td height="148" style="height:148px;width:216px;">Togni Reagent II</td>
			<td style="width:71px;"></td>
			<td style="width:119px;"></td>
			<td style="width:167px;">Prepared according to the literature procedure (ref 37). Caution: Pure Togni reagent II is impact and friction sensitive, treat it with great care (see ref. 36).</td>
		</tr>
		<tr height="64">
			<td height="64" style="height:64px;width:216px;">Tetrahydrofuran</td>
			<td style="width:71px;">BDH</td>
			<td style="width:119px;">BDH1149-4LG</td>
			<td style="width:167px;">Distilled from deep purple sodium benzophenone ketyl.</td>
		</tr>
		<tr height="64">
			<td height="64" style="height:64px;width:216px;">Diethyl Ether</td>
			<td style="width:71px;">Fisher Scientific</td>
			<td style="width:119px;">148221</td>
			<td style="width:167px;">Distilled from deep purple sodium benzophenone ketyl.</td>
		</tr>
		<tr height="47">
			<td height="47" style="height:47px;width:216px;">Chloroform</td>
			<td style="width:71px;">Fisher Scientific</td>
			<td style="width:119px;">141739</td>
			<td style="width:167px;">Dried over CaH2 and distilled</td>
		</tr>
		<tr height="47">
			<td height="47" style="height:47px;width:216px;">nitro methane</td>
			<td style="width:71px;">Alfa Aesar</td>
			<td style="width:119px;">J03z053</td>
			<td style="width:167px;">Dried over CaSO4 and distilled</td>
		</tr>
		<tr height="43">
			<td height="43" style="height:43px;width:216px;">Silica gel</td>
			<td style="width:71px;">SILICYCLE</td>
			<td style="width:119px;">60514</td>
			<td style="width:167px;">40-63 &#181;m (230-400 mesh)</td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:216px;">Cilite</td>
			<td style="width:71px;">EMD</td>
			<td style="width:119px;">2012040674</td>
			<td style="width:167px;">Not acid washed</td>
		</tr>
	</tbody>
</table>

protocol for the synthesis of ortho-trifluoromethoxylated aniline derivatives

Le molecole portanti trifluorometossi gruppo (OCF 3) spesso show desiderato proprietà farmacologiche e biologiche. Tuttavia, la sintesi di composti aromatici facile trifluoromethoxylated rimane una sfida formidabile nella sintesi organica. Approcci convenzionali spesso soffrono di portata substrato povero, o richiedono l&#39;uso di, manico difficili da altamente tossici, e / o reattivi termicamente labili. Qui riportiamo un protocollo di facile utilizzo per la sintesi di metil 4-acetamido-3- (trifluorometossi) benzoato utilizzando 1-trifluorometil-1,2-benziodoxol-3 (1H) -one (Togni reagente II). Trattamento metil 4- (N -hydroxyacetamido) benzoato (1a) con Togni reagente II in presenza di una quantità catalitica di carbonato di cesio (Cs 2 CO 3) in cloroformio a RT prestata metil 4- (N - (trifluorometossi) acetammido) benzoato (2a). Questo intermedio è stato poi convertito nel prodotto finale metil 4-acetamido-3- (trifluoromethoxy) benzoato (3a) in nitrometano a 120 ° C. Questa procedura è generale e può essere applicato alla sintesi di un ampio spettro di orto derivati ​​dell&#39;anilina -trifluoromethoxylated, che potrebbe servire come utili blocchi sintetici per la scoperta e lo sviluppo di nuovi prodotti farmaceutici, prodotti agrochimici e materiali funzionali.

Metil 4- (N -hydroxyacetamido) benzoato (1a) è stato sintetizzato nel 92% isolato resa attraverso una procedura in due fasi (ad esempio, la riduzione metil 4 nitrobenzoato con idrazina utilizzando 5% Rh / C come catalizzatore per formare metil 4- ( N -hydroxyamino) benzoato, seguita da protezione acetil della idrossilammina risultante). O- Trifluoromethylation di 1a con Togni reagente II in presenza di quantità catal...

Watch this Scientific Journal Video about Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives at JoVE.com

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Protocollo per la sintesi di<em&gt; Ortho</em&gt; Derivati ​​all&#39;anilina -trifluoromethoxylated

An operationally simple procedure for the synthesis of ortho-trifluoromethoxylated aniline derivatives via a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxyacetamide followed by thermally induced intramolecular OCF3-migration is reported.

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of ...

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Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

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9.8K Views.  State University of New York at Stony Brook. An operationally simple procedure for the synthesis of ortho-trifluoromethoxylated aniline derivatives via a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxyacetamide followed by thermally induced intramolecular OCF3-migration is reported.

Video: Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes

The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent reactions with azides to form cyanocarbene intermediates. The synthesis of hypervalent iodonium alkynyl triflates can be facile, but difficulties stem from their isolation and reactivity. In particular, the necessity to use filtration under inert atmosphere at -45 &deg;C for some HIATs requires special care and equipment. Once isolated, the compounds can be stored and used in reactions with azides to form cyanocarbene intermediates. 
The evidence for cyanocarbene generation is shown by visible extrusion of dinitrogen as well as the characterization of products that occur from O-H insertion, sulfoxide complexation, and cyclopropanation. A side reaction of the cyanocarbene formation is the generation of a vinylidene-carbene and the conditions to control this process are discussed. There is also potential to form a hypervalent iodonium alkenyl triflate and the means of isolation and control of its generation are provided. The O-H insertion reaction involves using a HIAT, sodium azide or tetrabutylammonium azide, and methanol as solvent/substrate. The sulfoxide complexation reaction uses a HIAT, sodium azide or tetrabutylammonium azide, and dimethyl sulfoxide as solvent. The cyclopropanations can be performed with or without the use of solvent. The azide source must be tetrabutylammonium azide and the substrate shown is styrene.

Herein is described the synthesis, isolation, and reactions of hypervalent iodonium alkynyl triflates (HIATs) with azides to generate cyanocarbenes. The procedures will involve air-sensitive and cryogen techniques, including cold filtration under an inert atmosphere. Handling and safety of the synthesized compounds will also be discussed.

Sintesi di hypervalent iodonio Alchinile triflati per l&#39;applicazione di Generazione Cyanocarbenes

The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent ...

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Chimica

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order to streamline synthesis by saving steps, time and material compared to conventional methods that require the introduction and removal of activating or directing groups. Therefore, the functionalization of C-H bonds is also attractive for green chemistry. Under oxidative conditions, two C-H bonds or one C-H and one heteroatom-H bond can be transformed to C-C and C-heteroatom bonds, respectively. Often these oxidative coupling reactions require synthetic oxidants, expensive catalysts or high temperatures. Here, we describe a two-step procedure to functionalize indole derivatives, more specifically tetrahydrocarbazoles, by C-H amination using only elemental oxygen as oxidant. The reaction uses the principle of C-H functionalization via Intermediate PeroxideS (CHIPS). In the first step, a hydroperoxide is generated oxidatively using visible light, a photosensitizer and elemental oxygen. In the second step, the N-nucleophile, an aniline, is introduced by Br&#248;nsted-acid catalyzed activation of the hydroperoxide leaving group. The products of the first and second step often precipitate and can be conveniently filtered off. The synthesis of a biologically active compound is shown.

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

A two-step procedure for the synthesis of pharmaceutically active indole-derivatives by C-H functionalization with anilines is described, using photo- and Br&#248;nsted acid catalysis.

Sintesi di derivati ​​antivirale Tetrahydrocarbazole da fotochimica e acido-catalizzata CH funzionalizzazione via intermedi perossidi (CHIPS)

The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order ...

A Direct, Early Stage Guanidinylation Protocol for the Synthesis of Complex Aminoguanidine-containing Natural Products

The guanidine functional group, displayed most prominently in the amino acid arginine, one of the fundamental building blocks of life, is an important structural element found in many complex natural products and pharmaceuticals. Owing to the continual discovery of new guanidine-containing natural products and designed small molecules, rapid and efficient guanidinylation methods are of keen interest to synthetic and medicinal organic chemists. Because the nucleophilicity and basicity of guanidines can affect subsequent chemical transformations, traditional, indirect guanidinylation is typically pursued. Indirect methods commonly employ multiple protection steps involving a latent amine precursor, such as an azide, phthalimide, or carbamate. By circumventing these circuitous methods and employing a direct guanidinylation reaction early in the synthetic sequence, it was possible to forge the linear terminal guanidine containing backbone of clavatadine A to realize a short and streamlined synthesis of this potent factor XIa inhibitor. In practice, guanidine hydrochloride is elaborated with a carefully constructed protecting array that is optimized to survive the synthetic steps to come. In the preparation of clavatadine A, direct guanidinylation of a commercially available diamine eliminated two unnecessary steps from its synthesis. Coupled with the wide variety of known guanidine protecting groups, direct guanidinylation evinces a succinct and efficient practicality inherent to methods that find a home in a synthetic chemist&#39;s toolbox.

Here, we present a protocol for direct, early stage guanidinylation that enables rapid total synthesis of aminoguanidine-containing small organic molecules. An advanced synthetic intermediate used in the synthesis of a blood coagulation factor XIa inhibitor was prepared using this protocol.

Un diretto, Early Stage Guanidinylation protocollo per la sintesi di complessi Aminoguanidine contenenti prodotti naturali

The guanidine functional group, displayed most prominently in the amino acid arginine, one of the fundamental building blocks of life, is an important ...

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

HKUST-1 come catalizzatore eterogeneo per la sintesi di vanillina

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately ...

A Protocol for the Production of Gliadin-cyanoacrylate Nanoparticles for Hydrophilic Coating

This article presents a protocol for the production of protein-based nanoparticles that changes the hydrophobic surface to hydrophilic by a simple spray coating. These nanoparticles are produced by the polymerization reaction of alkyl cyanoacrylate on the surface of cereal protein (gliadin) molecules. Alkyl cyanoacrylate is a monomer that instantly polymerizes at RT when it is applied to the surface of materials. Its polymerization reaction is initiated by the trace amounts of weakly basic or nucleophilic species on the surface, including moisture. Once polymerized, the polymerized alkyl cyanoacrylates show a strong affinity with the object materials because nitrile groups are in the backbone of poly (alkyl cyanoacrylate). Proteins also work as initiator for this polymerization because they contain amine groups that can initiate the polymerization of cyanoacrylate. If aggregated protein is used as an initiator, protein aggregate is surrounded by the hydrophobic poly(alkyl cyanoacrylate) chains after the polymerization reaction of alkyl cyanoacrylate. By controlling the experimental condition, particles in the nanometer range are produced. The produced nanoparticles readily adsorb to the surface of most materials including glass, metals, plastics, wood, leather, and fabrics. When the surface of a material is sprayed with the produced nanoparticle suspension and rinsed with water, the micellar structure of nanoparticle changes its conformation, and the hydrophilic proteins are exposed to the air. As a result, the nanoparticle-coated surface changes to hydrophilic.

This article presents a protocol for the production of protein-based nanoparticles that changes the hydrophobic surface to hydrophilic. The produced nanoparticle is an assembly of gliadin-cyanoacrylate diblock copolymers. Spray coating with the produced nanoparticle changes the surface of target material to a hydrophilic surface.

Un protocollo per la produzione di nanoparticelle gliadina-cianoacrilato per rivestimento idrofilo

This article presents a protocol for the production of protein-based nanoparticles that changes the hydrophobic surface to hydrophilic by a simple spray ...

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the development of antibody drug conjugates (ADCs) and nanomedicine, fluorescent microscopy and systems chemistry. For many of these applications, specificity of the bioconjugation method used is of prime concern. The Michael addition of maleimides with cysteine(s) on the target proteins is highly selective and proceeds rapidly under mild conditions, making it one of the most popular methods for protein bioconjugation.
We demonstrate here the modification of the only surface-accessible cysteine residue on yeast cytochrome c with a ruthenium(II) bisterpyridine maleimide. The protein bioconjugation is verified by gel electrophoresis and purified by aqueous-based fast protein liquid chromatography in 27% yield of isolated protein material. Structural characterization with MALDI-TOF MS and UV-Vis is then used to verify that the bioconjugation is successful. The protocol shown here is easily applicable to other cysteine - maleimide coupling of proteins to other proteins, dyes, drugs or polymers.

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

This protocol details the important steps required for the bioconjugation of a cysteine containing protein to a maleimide, including reagent purification, reaction conditions, bioconjugate purification and bioconjugate characterization.

Sintesi di proteine ​​bioconiugati<em&gt; via</em&gt; Chimica cisteina-maleimmide

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

Sintesi facile di micelle vermiforme dalla luce visibile mediata polimerizzazione in dispersione Utilizzando Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

Protocol for the Solid-phase Synthesis of Oligomers of RNA Containing a 2'-O-thiophenylmethyl Modification and Characterization via Circular Dichroism

Solid-phase synthesis has been used to obtain canonical and modified polymers of nucleic acids, specifically of DNA or RNA, which has made it a popular methodology for applications in various fields and for different research purposes. The procedure described herein focuses on the synthesis, purification, and characterization of dodecamers of RNA 5&#39;-[CUA CGG AAU CAU]-3&#39; containing zero, one, or two modifications located at the C2&#39;-O-position. The probes are based on 2-thiophenylmethyl groups, incorporated into RNA nucleotides via standard organic synthesis and introduced into the corresponding oligonucleotides via their respective phosphoramidites. This report makes use of phosphoramidite chemistry via the four canonical nucleobases (Uridine (U), Cytosine (C), Guanosine (G), Adenosine (A)), as well as 2-thiophenylmethyl functionalized nucleotides modified at the 2&#39;-O-position; however, the methodology is amenable for a large variety of modifications that have been developed over the years. The oligonucleotides were synthesized on a controlled-pore glass (CPG) support followed by cleavage from the resin and deprotection under standard conditions, i.e., a mixture of ammonia and methylamine (AMA) followed by hydrogen fluoride/triethylamine/N-methylpyrrolidinone. The corresponding oligonucleotides were purified via polyacrylamide electrophoresis (20% denaturing) followed by elution, desalting, and isolation via reversed-phase chromatography (Sep-pak, C18-column). Quantification and structural parameters were assessed via ultraviolet-visible (UV-vis) and circular dichroism (CD) photometric analysis, respectively. This report aims to serve as a resource and guide for beginner and expert researchers interested in embarking in this field. It is expected to serve as a work-in-progress as new technologies and methodologies are developed. The description of the methodologies and techniques within this document correspond to a DNA/RNA synthesizer (refurbished and purchased in 2013) that uses phosphoramidite chemistry.

Protocol for the Solid-phase Synthesis of Oligomers of RNA Containing a 2'-O-thiophenylmethyl Modification and Characterization via Circular Dichroism

This article provides a detailed procedure on the solid-phase synthesis, purification, and characterization of dodecamers of RNA modified at the C2&#39;-O-position. UV-vis and circular dichroism photometric analyses are used to quantify and characterize structural aspects, i.e., single-strands or double-strands.

Protocollo per la sintesi in fase solida di oligomeri di RNA contenente un 2&#39;-<em&gt; O</em&gt; -thiophenylmethyl Modifica e caratterizzazione attraverso il Dicroroo circolare

Solid-phase synthesis has been used to obtain canonical and modified polymers of nucleic acids, specifically of DNA or RNA, which has made it a popular ...

Synthesis and Mass Spectrometry Analysis of Oligo-peptoids

Peptoids are sequence-controlled peptide-mimicking oligomers consisting of N-alkylated glycine units. Among many potential applications, peptoids have been thought of as a type of molecular information storage. Mass spectrometry analysis has been considered the method of choice for sequencing peptoids. Peptoids can be synthesized via solid phase chemistry using a repeating two-step reaction cycle. Here we present a method to manually synthesize oligo-peptoids and to analyze the sequence of the peptoids using tandem mass spectrometry (MS/MS) techniques. The sample peptoid is a nonamer consisting of alternating N-(2-methyloxyethyl)glycine (Nme) and N-(2-phenylethyl)glycine (Npe), as well as an N-(2-aminoethyl)glycine (Nae) at the N-terminus. The sequence formula of the peptoid is Ac-Nae-(Npe-Nme)4-NH2, where Ac is the acetyl group. The synthesis takes place in a commercially available solid-phase reaction vessel. The rink amide resin is used as the solid support to yield the peptoid with an amide group at the C-terminus. The resulting peptoid product is subjected to sequence analysis using a triple-quadrupole mass spectrometer coupled to an electrospray ionization source. The MS/MS measurement produces a spectrum of fragment ions resulting from the dissociation of charged peptoid. The fragment ions are sorted out based on the values of their mass-to-charge ratio (m/z). The m/z values of the fragment ions are compared against the nominal masses of theoretically predicted fragment ions, according to the scheme of peptoid fragmentation. The analysis generates a fragmentation pattern of the charged peptoid. The fragmentation pattern is correlated to the monomer sequence of the neutral peptoid. In this regard, MS analysis reads out the sequence information of the peptoids.

A protocol is described for the manual synthesis of oligo-peptoids followed by sequence analysis by mass spectrometry.

Sintesi e analisi di spettrometria di massa di Oligo-peptoids

Peptoids are sequence-controlled peptide-mimicking oligomers consisting of N-alkylated glycine units. Among many potential applications, peptoids have ...

The MPLEx Protocol for Multi-omic Analyses of Soil Samples

Mass spectrometry (MS)-based integrated metaproteomic, metabolomic, and lipidomic (multi-omic) studies are transforming our ability to understand and characterize microbial communities in environmental and biological systems. These measurements are even enabling enhanced analyses of complex soil microbial communities, which are the most complex microbial systems known to date. Multi-omic analyses, however, do have sample preparation challenges, since separate extractions are typically needed for each omic study, thereby greatly amplifying the preparation time and amount of sample required. To address this limitation, a 3-in-1 method for the simultaneous extraction of metabolites, proteins, and lipids (MPLEx) from the same soil sample was created by adapting a solvent-based approach. This MPLEx protocol has proven to be both simple and robust for many sample types, even when utilized for limited quantities of complex soil samples. The MPLEx method also greatly enabled the rapid multi-omic measurements needed to gain a better understanding of the members of each microbial community, while evaluating the changes taking place upon biological and environmental perturbations.

A protocol is presented for simultaneously extracting metabolites, proteins, and lipids from a single soil sample, allowing reduced sample preparation times and enabling multi-omic mass spectrometry analyses of samples with limited quantities.

Il protocollo MPLEx Multi-omic nell'analisi di campioni di terreno

Mass spectrometry (MS)-based integrated metaproteomic, metabolomic, and lipidomic (multi-omic) studies are transforming our ability to understand and ...

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Sintesi di hypervalent iodonio Alchinile triflati per l'applicazione di Generazione Cyanocarbenes

Sintesi di derivati antivirale Tetrahydrocarbazole da fotochimica e acido-catalizzata CH funzionalizzazione via intermedi perossidi (CHIPS)

Un diretto, Early Stage Guanidinylation protocollo per la sintesi di complessi Aminoguanidine contenenti prodotti naturali

HKUST-1 come catalizzatore eterogeneo per la sintesi di vanillina

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Protocollo per la sintesi in fase solida di oligomeri di RNA contenente un 2'-

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Un diretto, Early Stage Guanidinylation protocollo per la sintesi di complessi Aminoguanidine contenenti prodotti naturali

HKUST-1 come catalizzatore eterogeneo per la sintesi di vanillina

Un protocollo per la produzione di nanoparticelle gliadina-cianoacrilato per rivestimento idrofilo

Sintesi di proteine ​​bioconiugati

Sintesi facile di micelle vermiforme dalla luce visibile mediata polimerizzazione in dispersione Utilizzando Photoredox Catalyst

Protocollo per la sintesi in fase solida di oligomeri di RNA contenente un 2'-

Sintesi e analisi di spettrometria di massa di Oligo-peptoids

Il protocollo MPLEx Multi-omic nell'analisi di campioni di terreno

Sintesi di derivati antivirale Tetrahydrocarbazole da fotochimica e acido-catalizzata CH funzionalizzazione via intermedi perossidi (CHIPS)

Sintesi di proteine bioconiugati