Os autores agradecem a Deutsche Forschungsgemeinschaft, Bayer Pharma AG, Chemtura Organometallics GmbH Bergkamen, Bayer Services GmbH, a BASF AG, e Sasol GmbH para apoio financeiro.

1. Preparação de titânio (IV) Solução de terc -butoxide/Triethylchlorosilane <ol><li> Dissolve-se 400 mg (400 ul) de titânio (IV), terc-butóxido de potássio (1 mmol) em 10 ml de diclorometano seco. Adicionar 150 mg (170 ul) trietilclorosilano (1 mmol) a esta solução à temperatura ambiente. 1 ml desta solução de diclorometano contém 0,1 mmol de titânio (IV), terc-butóxido de potássio e 0,1 mmol trietilclorosilano. </li></ol> 2. Pinacol-reacção de tetrafenil-1 ,2-etanodiol (1) com 2-Ethylbutyraldehyde <ol><li> Resolver 366 mg de tetrafenil-1 ,2-etanodiol (1, 1 mmol) e 300 mg (370 mL), recentemente destilado de 2-ethylbutyraldehyde (3 mmol) em 3 ml de diclorometano seco. </li><li> Adicionar 0,5 ml de titânio preparado separadamente (IV), terc -butoxide/triethylchlorosilane solução (0,05 mmol). </li><li> Agita-se a mistura resultante à TA, num tubo de reacção selado. </li><li> Confirm a reacção está completa através de cromatografia de camada fina (eluente: hexano / acetona - 1/9) sobre gel de sílica placas de TLC (60 F254). O fim da reacção é atingido no momento tetrafenil-1 ,2-etanodiol 1 já não pode ser detectado (~ 12 horas). O valor de Rf do produto é de 0,3 14. </li><li> Dilui-se a mistura de reacção resultante com 50 ml de diclorometano. </li><li> Lava-se a mistura de reacção diluída sucessivamente por 20 ml de solução saturada de cloreto de amónio aquoso e solução de carbonato de hidrogénio de sódio num funil de separação. </li><li> Isolar a camada orgânica por um funil de separação. </li><li> Seca-se a camada orgânica por meio de agitação com sulfato de magnésio seco. </li><li> Filtre a suspensão por um filtro de papel de pregas e recolher os filtrados. </li><li> Retirar diclorometano do filtrado em vácuo a 40 ° C utilizando um evaporador rotativo (10-30 mmHg). A evaporação dos solventes exigirá 20 min. </li><li> Purifica-se o resíduo remanescentepor cromatografia em coluna intermitente através de uma coluna de gel de sílica (0,035-0,070 mm, ACROS) com um gradiente de hexano / acetona (a partir das 19:01 e vai até 16:04) para adquirir 280 mg de 1,2-diol 2f (0,99 mmol). </li><li> Confirmar a identidade do 2f 1,2-diol por 1 H espectroscopia de ressonância magnética nuclear (RMN) usando CDCI3 como solvente. Para um espectrómetro de RMN de 300 MHz, o espectro de 1 H RMN do diol é a seguinte: δ = 0,78 (t, 3H, J = 7,4 Hz), 0,87 (t, 3H, J = 7,3 Hz), 1,18-1,40 (m , 4H), 1,75-1,81 (m, 1H), 1,91 (s, 1H, OH), 3,12 (s, 1H, OH), 4,68 (d, 1H, J = 1,2 Hz), 7,19-7,37 (m, 6H ), 7,44-7,46 (m, 2H), 7,61-7,63 (m, 2H). </li></ol> 3. Pinacol-reacção de tetrafenil-1 ,2-etanodiol (1) com dietil cetona <ol><li> Resolver 366 mg de tetrafenil-1 ,2-etanodiol (1, 1 mmol) e 345 mg (423 mL) de éter-cetona (4 mmol) em 3ml de diclorometano seco. </li><li> Adicionar 1 ml de titânio preparado separadamente (IV) Solução de terc -butoxide/triethylchloro-silane (0,1 mmol). </li><li> Agita-se a mistura resultante à TA, num tubo de reacção selado. </li><li> Confirmar a reacção está completa através de cromatografia de camada fina (eluente: hexano / acetona, 9:1) em gel de sílica (placas de TLC de 60 F254). O fim da reacção é atingido no tempo, quando tetrafenil-1 ,2-etanodiol 1 não pode ser detectada (~ 12 horas). O Rf do produto é de 0,3 14. </li><li> Dilui-se a mistura de reacção resultante com 50 ml de diclorometano. </li><li> Lava-se a mistura de reacção diluída sucessivamente por 20 ml de solução saturada de cloreto de amónio aquoso e solução de carbonato de sódio num funil de separação. </li><li> Isolar a camada orgânica por um funil de separação. </li><li> Seca-se a camada orgânica por meio de agitação com sulfato de magnésio seco. </li><li> Filtre a suspensão por um fil papel caneladoter e recolher os filtrados. </li><li> Retirar diclorometano in vácuo a 40 ° C utilizando um evaporador rotativo (10-30 mmHg). A evaporação dos constituintes voláteis exigirá 30 min. </li><li> Purifica-se o resíduo restante por cromatografia em coluna intermitente através de uma coluna de gel de sílica (0,035-0,070 mm, ACROS) com um gradiente de hexano / acetona (a partir das 19:01 e vai até 16:04) para adquirir a 250 mg de 1, 4f 2-diol (0,93 mmol). </li><li> Confirmam a identidade do produto por 1H espectroscopia de ressonância magnética nuclear (RMN) usando CDCI3 como solvente. Para um espectrómetro de RMN de 300 MHz, o espectro de 1 H RMN do 4f diol é a seguinte: δ = 0,92 (t, 6H, J = 7,6 Hz), 1,78 (m, 4H), 2,03 (s, 1H, OH), 2,83 (s, 1H, OH), 7,26-7,35 (m, 6H), 7,69-7,71 (m, 4H). </li></ol>

<ol>
	<li>Hirao, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Catalytic+reductive+coupling+of+carbonyl+compounds+-+The+pinacol+coupling+reaction+and.">Catalytic reductive coupling of carbonyl compounds - The pinacol coupling reaction and.</a> 279, 53-75 (2007).</li><li>Chatterjee, A., Joshi, N. N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Evolution+of+the+stereoselective+pinacol+coupling+reaction.">Evolution of the stereoselective pinacol coupling reaction.</a> Tetrahedron. 62, 12137-12158 (2006).</li><li>Ladipo, F. 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B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Convenient+synthesis+of+unsymmetrical+pinacols+by+coupling+of+structurally+similar+aromatic+aldehydes+mediated+by+low-valent+titanium.">A Convenient synthesis of unsymmetrical pinacols by coupling of structurally similar aromatic aldehydes mediated by low-valent titanium.</a> Synthesis. , 277-282 (2009).</li><li>Paquette, L. A., Lai, K. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Pinacol+macrocyclization-based+route+to+the+polyfused+medium-sized+CDE+ring+system+of+lancifodilactone.">Pinacol macrocyclization-based route to the polyfused medium-sized CDE ring system of lancifodilactone.</a> G. Org. Lett. 10, 3781-3784 (2008).</li><li>Maekawa, H., Yamamoto, Y., Shimada, H., Yonemura, K., Nishiguchi, I. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mg-+promoted+mixed+pinacol+coupling.">Mg- promoted mixed pinacol coupling.</a> Tetrahedron Lett. 45, 3869-3872 (2004).</li><li>Kang, M., Park, J., Pedersen, S. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Pinacol+cross+coupling+reactions+of+ethyl+2-alkyl-2-formylpropionates.+stereoselective+synthesis+of+2,2,4-+trialkyl-3-hydroxy-&#947;-butyrolactones.">Pinacol cross coupling reactions of ethyl 2-alkyl-2-formylpropionates. stereoselective synthesis of 2,2,4- trialkyl-3-hydroxy-&#947;-butyrolactones.</a> Syn. Lett. , 41-43 (1997).</li><li>Askham, F. R., Carroll, K. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Anionic+zirconaoxiranes+as+nucleophilic+aldehyde+equivalents.+application+to+intermolecular+pinacol+cross+coupling.">Anionic zirconaoxiranes as nucleophilic aldehyde equivalents. application to intermolecular pinacol cross coupling.</a> J. Org. Chem. 58, 7328-7329 (1993).</li><li>Hou, Z., Takamine, K., Aoki, O., Shiraishi, H., Fujiwara, Y., Taniguchi, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nucleophilic+Addition+of+lanthanoid+metal+umpoled+diaryl+ketones+to+electrophiles.">Nucleophilic Addition of lanthanoid metal umpoled diaryl ketones to electrophiles.</a> J. Org. Chem. 53, 6077-6084 (1988).</li><li>Groth, U., Jung, M., Vogel, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Intramolecular+chromium(II)-catalyzed+pinacol+cross+coupling+of+2-Mmethylene-&#945;,&#969;-dicarbonyls.">Intramolecular chromium(II)-catalyzed pinacol cross coupling of 2-Mmethylene-&#945;,&#969;-dicarbonyls.</a> Syn. Lett. , 1054-1058 (2004).</li><li>Appendino, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+Modified+Ingenol+Esters.">Synthesis of Modified Ingenol Esters.</a> Eur. J. Org. Chem. , 3413-3420 (1999).</li><li>Spaccini, R., Pastori, N., Clerici, A., Punta, C., Porta, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Key+role+of+Ti(IV)+in+the+selective+radical-radical+cross-coupling+mediated+by+the+Ingold-Fischer+effect.">Key role of Ti(IV) in the selective radical-radical cross-coupling mediated by the Ingold-Fischer effect.</a> J. Am. Chem. Soc. 130, 18018-18024 (2008).</li><li>Leonard, J., Lyfo, B., Procter, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Advanced Practical Organic Chemistry. , (2013).</li><li>Scheffler, U., Stoesser, R., Mahrwald, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Retropinacol+/+cross-pinacol+coupling+reactions+-+a+catalytic+access+to+1,2-unsymmetrical+diols.">Retropinacol / cross-pinacol coupling reactions - a catalytic access to 1,2-unsymmetrical diols.</a> Adv. Synth. Cat. 354, 2648-2652 (2012).</li></ol>

Os autores declaram não haver interesses financeiros concorrentes.

Uma diminuição global em tempos de reação e rendimentos mais elevados é observado por implantação de compostos carbonílicos rico em elétrons (compare entrada 3 com 17, Tabela 1 ou entrada de 19 com 13, Tabela 2). Além disso, em reacções de cetonas com substituintes volumosos um decréscimo no rendimento é observada sob condições comparáveis ​​(comparar entrada 12 com 11, Tabela 2). Apesar de um...

A reacção de acoplamento de pinacol é um método geral e de uso geral para a preparação dos dióis vicinais simetricamente (1,2-dióis, pinacols). Para revisões globais neste domínio ver referências Hirao 1, Chatterjee e Joshi 2, Ladipo 3 e Gansäuer e Bluhm 4. Em contraste a isso, apenas alguns relatos publicados referem-se a uma realização eficiente das reacções de acoplamento cruzado do pinacol para dar os correspondentes 1,2-dióis simétricos (de titânio (IV) / cloreto de manganês 5, samário (II) iodeto de 6, magnésio / trimetilclorossilano 7, vanádio (II), 8, zircónio / estanho 9, itérbio e 10). Assim, a reacção de acoplamento cruzado de pinacol intermoleculares ainda continua a ser um grande desafio em química orgânica, em especial a realização desta transformação catalítica. A formação de produtos de acoplamento cruzado é cineticamente disfavoredsob condições de acoplamento de pinacol clássica. Para obter quantidades suficientes do produto assimétrico retardada adição de um composto de carbonilo é possível. Existem alguns exemplos que estão a desenvolver este conceito, mas eles são baseados em várias manipulações experimentais específicas e, portanto, não podem ser generalizados. Além disso, o excesso requerido de um composto de carbonilo nestas transformações resultou numa separação trabalhosa de uma mistura complexa de produtos 11. Uma alternativa para esta finalidade é representado pela precomplexation de um reagente render quantidades equimolares de um reagente adicional necessário. Vários exemplos de uma reacção reversível pinacol foram descritos 12. Estes levam à consideração de que tais condições podem ser um ponto de partida ideal para a síntese seletiva de produtos de acoplamento cruzado. Uma vez que um metal de baixa valência, bem como uma espécie radical reactivo é formado simultaneamente in situ, Dióis simétricos pode ser formado exclusivamente na presença de um reagente de carbonilo adequado. Ao melhor de nosso conhecimento de tal método não tem sido relatada antes (Porta et al. Descreveu uma clivagem pinacol comparável e acoplamento posterior pela implantação adicional de quantidades estequiométricas de AIBN (2,2 &#39;-azo-bis-isobutironi) para gerar os radicais necessários 13). Nisto um protocolo é visualizado que fornece um acesso rápido e operacionalmente simples assimétricas 1,2-dióis. Os produtos são principalmente pinacol assimétricos acessível com excelentes rendimentos (&gt; 95%). Indesejados produtos simetricamente pinacol não são observadas. Esta nova metodologia cross-pinacol é baseada em uma seqüência de acoplamento retropinacol / cross-pinacol. Será demonstrado a seguir por meio de reacções representativos de benzopinacole (1,1,2,2-tetrafenil-1 ,2-etanodiol, 1) com 2-ethylbutyraldehyde (na série de aldeído) e wdiethylketone om (na série de cetona).

<table border="0" cellpadding="0" cellspacing="0">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:363px;">1.2-Dichloromethane</td>
			<td style="width:179px;">Sigma-Aldrich</td>
			<td style="width:137px;">319929</td>
			<td style="width:79px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Titanium(IV)tert-butoxide</td>
			<td>VWR International</td>
			<td>200014-852</td>
			<td style="width:79px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">2-Ethylbutyraldehyde</td>
			<td>Sigma-Aldrich</td>
			<td>110094</td>
			<td style="width:79px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Benzopinacol</td>
			<td>Aldrich</td>
			<td>B9807</td>
			<td style="width:79px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Triethylchlorosilane</td>
			<td>Aldrich</td>
			<td>&#160;235067</td>
			<td style="width:79px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">hexane, certified ACS</td>
			<td>Fisher scientific</td>
			<td>H29220</td>
			<td style="width:79px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">acetone, certified ACS</td>
			<td>ACROS</td>
			<td>42324</td>
			<td style="width:79px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Ammonium chloride</td>
			<td>ACROS</td>
			<td>19997</td>
			<td style="width:79px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Sodium hydrogen carbonate</td>
			<td>ACROS</td>
			<td>12336</td>
			<td style="width:79px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Magnesium sulphate</td>
			<td>ACROS</td>
			<td>41348</td>
			<td style="width:79px;"></td>
		</tr>
		<tr height="26">
			<td height="26" style="height:26px;">silica gel 60 F254 TLC plates</td>
			<td>VWR International</td>
			<td>1,057,140,001</td>
			<td style="width:79px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">&#160;silica gel, 0.035-0.070 for flash-chromatography</td>
			<td>ACROS</td>
			<td>240360300</td>
			<td style="width:79px;"></td>
		</tr>
	</tbody>
</table>

retropinacol/cross-pinacol coupling reactions - a catalytic access to 1,2-unsymmetrical diols

Assimétricos 1,2-dióis são dificilmente acessíveis por processos de acoplamento de pinacol redutivas. A execução bem sucedida de uma tal transformação está vinculado a um claro reconhecimento e diferenciação estrita de dois compostos carbonílicos semelhantes (aldeídos → secundárias 1,2-dióis ou cetonas → terciárias 1,2-dióis). Este ajuste fino ainda é um desafio e um problema não resolvido por um químico orgânico. Existem vários relatórios sobre a execução bem sucedida dessa transformação, mas eles não podem ser generalizados. Aqui nós descrevemos um processo de acoplamento catalítico direto pinacol que procede por meio de uma seqüência de acoplamento retropinacol / cross-pinacol. Assim, não simétricos 1,2-dióis substituídos podem ser acedidas com rendimentos quase quantitativos por meio de um desempenho operacionalmente simples sob condições muito suaves. Técnicas artificiais, tais como técnicas de seringa-bomba ou adições retardada de reagentes não são necessárias. O procedimento que descrevemos oferece um muito rápido acesso aprodutos cross-pinacol (1,2-dióis, dióis vicinais). Uma nova prorrogação desse novo processo, por exemplo, um desempenho enantiosseletiva poderia fornecer uma ferramenta muito útil para a síntese de assimétricas quirais 1,2-dióis.

Em reacções de tetrafenil-1 ,2-etanodiol 1 e acetona na presença de quantidades catalíticas de titânio (IV)-alcóxidos foi observada a formação de 1,1-difenil-1 ,2-diol 4a e ao mesmo tempo a formação de benzofenona-3 (Esquema 1). A simétrico 1,2-diol correspondente formada por um acoplamento de pinacol competitiva da acetona não foi detectada. No entanto, para obter conversões quantitativas tempos de reacção extremamente longos e inaceitáveis ​​foram ...

Watch this Scientific Journal Video about Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols at JoVE.com

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Uma nova conta para a síntese de 1,2-dióis simétricos com base num mecanismo de acoplamento retropinacol / cruzada pinacol descrito. Devido à execução desta reacção catalítica de uma melhoria considerável em relação às ligações cruzadas do pinacol convencionais é alcançado.

Retropinacol / Cross-pinacol reações de acoplamento - A Acesso Catalítica para 1,2-assimétricos Dióis

Unsymmetrical 1,2-diols are hardly accessible by reductive pinacol coupling processes. A successful execution of such a transformation is bound to a clear ...

retropinacolcross-pinacol-coupling-reactions-catalytic-access-to-12

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12.9K visualizações.  Humboldt University of Berlin.  Uma nova conta para a síntese de 1,2-dióis simétricos com base num mecanismo de acoplamento retropinacol / cruzada pinacol descrito. Devido à execução desta reacção catalítica de uma melhoria considerável em relação às ligações cruzadas do pinacol convencionais é alcançado. 

Vídeo: Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family of easy accessible, very cheap, and air stable, but highly active and universally applicable C-C cross-coupling catalysts with an excellent functional group tolerance. Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1), the least stable complex within this series towards protons; e.g. in the form of water, allows an eased nanoparticle formation and hence, proved to be the most active Heck catalyst within this series at 100 &#176;C and is a very rare example of an effective and versatile catalyst system that efficiently operates under mild reaction conditions. Rapid and complete catalyst degradation under work-up conditions into phosphonates, piperidinium salts and other, palladium-containing decomposition products assure an easy separation of the coupling products from catalyst and ligands. The facile, cheap, and rapid synthesis of 1,1',1"-(phosphinetriyl)tripiperidine and 1 respectively, the simple and convenient use as well as its excellent catalytic performance in the Heck reaction at 100 &#176;C make 1 to one of the most attractive and greenest Heck catalysts available.
We provide here the visualized protocols for the ligand and catalyst syntheses as well as the reaction protocol for Heck reactions performed at 10 mmol scale at 100 &#176;C and show that this catalyst is suitable for its use in organic syntheses.

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1&#039;,1&#039;&#039;-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions

Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1) is an easy accessible, cheap, and air stable, but highly active Heck catalyst with an excellent functional group tolerance that efficiently operates under mild reaction conditions to give the coupling products in very high yields.

Mizoroki-Heck Reações de acoplamento cruzado catalisado por Dicloro {bis [1,1 &#39;, 1&#39;&#39; - (phosphinetriyl) tripiperidine]} paládio sob condições de reação leves

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family ...

Química

Hot Biological Catalysis: Isothermal Titration Calorimetry to Characterize Enzymatic Reactions

Isothermal titration calorimetry (ITC) is a well-described technique that measures the heat released or absorbed during a chemical reaction, using it as an intrinsic probe to characterize virtually every chemical process. Nowadays, this technique is extensively applied to determine thermodynamic parameters of biomolecular binding equilibria. In addition, ITC has been demonstrated to be able of directly measuring kinetics and thermodynamic parameters (kcat, KM, &#916;H) of enzymatic reactions, even though this application is still underexploited. As heat changes spontaneously occur during enzymatic catalysis, ITC does not require any modification or labeling of the system under analysis and can be performed in solution. Moreover, the method needs little amount of material. These properties make ITC an invaluable, powerful and unique tool to study enzyme kinetics in several applications, such as, for example, drug discovery.
In this work an experimental ITC-based method to quantify kinetics and thermodynamics of enzymatic reactions is thoroughly described. This method is applied to determine kcat and KM of the enzymatic hydrolysis of urea by Canavalia ensiformis (jack bean) urease. Calculation of intrinsic molar enthalpy (&#916;Hint) of the reaction is performed. The values thus obtained are consistent with previous data reported in literature, demonstrating the reliability of the methodology.

Isothermal titration calorimetry measures heat flow released or absorbed in chemical reactions. This method can be used to quantify enzyme-catalysis. In this paper, the protocol for instrumental setup, experiment running, and data analysis is generally described, and applied to the characterization of enzymatic urea hydrolysis by jack bean urease.

Hot Catálise Biológica: Calorimetria isotérmica de titulação para caracterizar reações enzimáticas

Isothermal titration calorimetry (ITC) is a well-described technique that measures the heat released or absorbed during a chemical reaction, using it as ...

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand.

This protocol describes the use of amide coupling reactions of isonicotinic acid and diaminoalkanes to form bridging ligands suitable for use in the synthesis of multinuclear platinum complexes, which combine aspects of the anticancer drugs BBR3464 and picoplatin.

Acoplamento de amida de reacção para a síntese de ligandos baseados em Bispyridine e sua complexação com platina como agentes anticancerígenos dinucleares

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. ...

Real-time Monitoring of Reactions Performed Using Continuous-flow Processing: The Preparation of 3-Acetylcoumarin as an Example

By using inline monitoring, it is possible to optimize reactions performed using continuous-flow processing in a simple and rapid way. It is also possible to ensure consistent product quality over time using this technique. We here show how to interface a commercially available flow unit with a Raman spectrometer. The Raman flow cell is placed after the back-pressure regulator, meaning that it can be operated at atmospheric pressure. In addition, the fact that the product stream passes through a length of tubing before entering the flow cell means that the material is at RT. It is important that the spectra are acquired under isothermal conditions since Raman signal intensity is temperature dependent. Having assembled the apparatus, we then show how to monitor a chemical reaction, the piperidine-catalyzed synthesis of 3-acetylcoumarin from salicylaldehyde and ethyl acetoacetate being used as an example. The reaction can be performed over a range of flow rates and temperatures, the in-situ monitoring tool being used to optimize conditions simply and easily.

Real-time monitoring allows for fast optimization of reactions performed using continuous-flow processing. Here the preparation of 3-acetylcoumarin is used as an example. The apparatus for performing in-situ Raman monitoring is described, as are the steps required to optimize the reaction.

Monitoramento em tempo real de Reações realizada utilizando processamento de fluxo contínuo: A Preparação de 3-Acetylcoumarin como Exemplo

By using inline monitoring, it is possible to optimize reactions performed using continuous-flow processing in a simple and rapid way. It is also possible ...

Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form catalytically active N-Heterocyclic Carbenes (NHCs). Here we have used ILs as precatalysts in the addition of &#945;,&#946;-unsaturated aldehydes to chalcones to form 1,6-ketoesters, incorporating an anti-diphenyl moiety in a highly stereoselective fashion. The reaction has a broad substrate scope and several functional groups and heteroaromatics can be integrated into the ketoester backbone in generally good yields with maintained stereoselectivity. The reaction protocol is robust and scalable. The starting materials are inexpensive and the products can be obtained after simple filtration, avoiding solvent-demanding chromatography. Furthermore, the IL can be recycled up to 5 times without any loss of reactivity. Moreover, the 1,6-ketoester end product is a potent gelator in several hydrocarbon based solvents. The method enables rapid access to and evaluation of a new class of low molecular weight gelators (LMWGs) from recyclable and inexpensive starting materials.

Ionic liquids (ILs) mediate fast, simple and cheap access to 1,6-ketoesters in high diastereoselectivities and good yields. The reaction protocol is robust and the 1,6-ketoesters can be obtained in gram scale after a simple filtration protocol. Moreover, the 1,6-ketoesters are potent gelators in hydrocarbon solvents.

Síntese altamente Stereoselective de 1,6-cetoésteres Mediada por líquidos iônicos: A reacção de três componente permitindo o rápido acesso a uma nova classe de baixo peso molecular Gelators Peso

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form ...

A Simple, Low-cost, and Robust System to Measure the Volume of Hydrogen Evolved by Chemical Reactions with Aqueous Solutions

There is a growing research interest in the development of portable systems which can deliver hydrogen on-demand to proton exchange membrane (PEM) hydrogen fuel cells. Researchers seeking to develop such systems require a method of measuring the generated hydrogen. Herein, we describe a simple, low-cost, and robust method to measure the hydrogen generated from the reaction of solids with aqueous solutions. The reactions are conducted in a conventional one-necked round-bottomed flask placed in a temperature controlled water bath. The hydrogen generated from the reaction in the flask is channeled through tubing into a water-filled inverted measuring cylinder. The water displaced from the measuring cylinder by the incoming gas is diverted into a beaker on a balance. The balance is connected to a computer, and the change in the mass reading of the balance over time is recorded using data collection and spreadsheet software programs. The data can then be approximately corrected for water vapor using the method described herein, and parameters such as the total hydrogen yield, the hydrogen generation rate, and the induction period can also be deduced. The size of the measuring cylinder and the resolution of the balance can be changed to adapt the setup to different hydrogen volumes and flow rates.

The study of methods to generate on-demand hydrogen for fuel cells continues to grow in importance. However, systems to measure hydrogen evolution from the reaction of chemicals with water can be complicated and expensive. This article details a simple, low-cost, and robust method to measure the evolution of hydrogen gas.

Um simples, de baixo custo e sistema robusto para medir o volume de hidrogênio desprendido por reacções químicas com soluções aquosas

There is a growing research interest in the development of portable systems which can deliver hydrogen on-demand to proton exchange membrane (PEM) ...

Laboratory Production of Biofuels and Biochemicals from a Rapeseed Oil through Catalytic Cracking Conversion

The work is based on a reported study which investigates the processability of canola oil (bio-feed) in the presence of bitumen-derived heavy gas oil (HGO) for production of transportation fuels through a fluid catalytic cracking (FCC) route. Cracking experiments are performed with a fully automated reaction unit at a fixed weight hourly space velocity (WHSV) of 8 hr-1, 490-530 &#176;C, and catalyst/oil ratios of 4-12 g/g. When a feed is in contact with catalyst in the fluid-bed reactor, cracking takes place generating gaseous, liquid, and solid products. The vapor produced is condensed and collected in a liquid receiver at -15 &#176;C. The non-condensable effluent is first directed to a vessel and is sent, after homogenization, to an on-line gas chromatograph (GC) for refinery gas analysis. The coke deposited on the catalyst is determined in situ by burning the spent catalyst in air at high temperatures. Levels of CO2 are measured quantitatively via an infrared (IR) cell, and are converted to coke yield. Liquid samples in the receivers are analyzed by GC for simulated distillation to determine the amounts in different boiling ranges, i.e., IBP-221 &#176;C (gasoline), 221-343 &#176;C (light cycle oil), and 343 &#176;C+ (heavy cycle oil). Cracking of a feed containing canola oil generates water, which appears at the bottom of a liquid receiver and on its inner wall. Recovery of water on the wall is achieved through washing with methanol followed by Karl Fischer titration for water content. Basic results reported include conversion (the portion of the feed converted to gas and liquid product with a boiling point below 221 &#176;C, coke, and water, if present) and yields of dry gas (H2-C2's, CO, and CO2), liquefied petroleum gas (C3-C4), gasoline, light cycle oil, heavy cycle oil, coke, and water, if present.

This paper presents an experimental method to produce biofuels and biochemicals from canola oil mixed with a fossil-based feed in the presence of a catalyst at mild temperatures. Gaseous, liquid, and solid products from a reaction unit are quantified and characterized. Conversion and individual product yields are calculated and reported.

Produção Laboratório de Biocombustíveis e Bioquímicos de um óleo de colza por meio de Craqueamento Catalítico Conversão

The work is based on a reported study which investigates the processability of canola oil (bio-feed) in the presence of bitumen-derived heavy gas oil ...

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic nature of the monomer is conserved. The resulting polymer, polynorbornene, has a very high glass transition temperature, Tg, and interesting optical and electrical properties. However, the polymerization of functional norbornenes by this mechanism is complicated by the fact that the endo substituted norbornene monomer has, in general, a very low reactivity. Furthermore, the separation of the endo substituted monomer from the exo monomer is a tedious task. Here, we present a simple protocol for the polymerization of substituted norbornenes (endo:exo ca. 80:20) bearing either a carboxylic acid or a pendant double bond. The process does not require that both isomers be separated, and proceeds with low catalyst loadings (0.01 to 0.02 mol%). The polymer bearing pendant double bonds can be further transformed in high yield, to afford a polymer bearing pendant epoxy groups. These simple procedures can be applied to prepare polynorbornenes with a variety of functional groups, such as esters, alcohols, imides, double bonds, carboxylic acids, bromo-alkyls, aldehydes and anhydrides.

We describe the catalytic insertion polymerization of 5-norbornene-2-carboxylic acid and 5-vinyl-2-norbornene to form functional polymers with a very high glass transition temperature.

Um protocolo simples e eficiente para a polimerização por inserção catalítica de norbornenos funcionais

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic ...

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents

Organolithium reagents are powerful tools in the synthetic chemist&#39;s toolbox. However, the extreme pyrophoric nature of the most reactive reagents warrants proper technique, thorough training, and proper personal protective equipment. To aid in the training of researchers using organolithium reagents, a thorough, step-by-step protocol for the safe and effective use of tert-butyllithium on an inert gas line or within a glovebox is described. As a model reaction, preparation of lithium tert-butyl amide by the reaction of tert-butyl amine with one equivalent of tert-butyl lithium is presented.

The safe and proper use of organolithium reagents is described.

Um protocolo para reações seguras litiação Usando organolï¿½io Reagentes

Organolithium reagents are powerful tools in the synthetic chemist&#39;s toolbox. However, the extreme pyrophoric nature of the most reactive reagents ...

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. Detailed and generalized protocols are also presented for testing the catalytic activity of such complexes in arylation and Suzuki-Miyaura cross-coupling reactions. Representative results are shown for the catalytic activity of the four complexes in arylation and Suzuki-Miyaura type reactions. For each of the reactions investigated, at least one of the four complexes successfully catalyzed the reaction, qualifying them as promising candidates for catalysis of many carbon-carbon bond-forming reactions. The protocols presented are general enough to be adapted for the synthesis, purification and catalytic activity testing of new palladium N-heterocyclic carbene complexes.

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. The complexes were tested for catalytic activity in arylation and Suzuki-Miyaura reactions. For each reaction investigated, at least one of the four complexes successfully catalyzed the reaction.

Complexos de paládio N-heterocíclicos de carbeno: síntese a partir de sais de benzimidazólio e atividade catalítica em reações de formação de ligações carbono-carbono

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from ...