RAF thanks the National Science Foundation (CHE-0844946) for support of this work.

1. Synthesis of SmI2 (0.1 M)
<ol>
 <li>Flame dry a 50 ml round bottomed flask and flush it with argon. Add a stir bar and cover the flask with septa. Weigh out samarium metal (0.2 g, 1.3 mmol) and add to flask, again flushing the flask with argon.</li>
 <li>Add 10 ml dry, thoroughly degassed tetrahydrofuran (THF) followed by iodine crystals (0.254 g, 2.0 mmol). Add an argon balloon through the septum; this keeps a positive pressure of Ar atmosphere on the reaction.</li>
 <li>Stir the solution vigorously at room temperature for over 3 hr. As SmI2 is generated the solution passes through a variety of color changes; orange followed by yellow (45 min), and green (1 hr) which eventually turns into blue.</li>
 <li>The final navy blue color is indication that singly ionized samarium has formed. In order to ensure full conversion, stir the solution for at least 3 hr before using SmI2 in synthesis.</li>
</ol>
2. Samarium Barbier Reaction-hexamethylphosphoramide (HMPA) Addition
<ol>
 <li>To make the SmI2-HMPA complex, take the freshly prepared SmI2 under argon (10 ml, 0.1 M, 1.0 mmol) and add 1.75 ml of HMPA (10 equiv., 10 mmol) through a syringe, dropwise, under argon. A deep purple color forms.</li>
 <li>Separately in a clean, dry vial under argon, add iodododecane (0.45 mmol, 110 &mu;l), 3-pentanone (0.45 mmol, 48 &mu;l) and 2 ml of dried THF.</li>
 <li>Add the substrate solution mixture dropwise to the SmI2/HMPA complex.</li>
 <li>Within 5 min of stirring, the purple color will start to look cloudy, indicating the end of the reaction.</li>
 <li>After the reaction is complete, expose the solution to air to quench it; upon stirring the color further changes to yellow.</li>
 <li>The reaction is then worked up by washing with saturated aqueous ammonium chloride. Add the solution to a separatory funnel and add diethylether (5 ml). After vigorous shaking remove the top organic layer, add more diethyl ether. Extract from the aqueous layer two more times and then combine all of the organic layers.</li>
 <li>Wash the organic layer with a saturated solution of aqueous sodium thiosulfate. Remove the bottom aqueous layer, followed by wash with water and then final wash with brine. Obtain the top organic layer and add magnesium sulfate to soak up any last amount of water present in the solution.</li>
 <li>Pass the solution through a plug of Florisil in order to remove excess HMPA.</li>
 <li>Concentrate the solution on a rotary evaporator to obtain Barbier product. The product was identified by GCMS and 1H NMR.23</li>
</ol>
3. Samarium Barbier Reaction-Ni(acac)2 Catalyst
<ol>
 <li>Weigh out Ni(acac)2 (1 mol%, 0.01 mmol, 0.0026 g) and add to a clean, dry vial containing 3 ml of degassed THF, under argon. Add the Ni(acac)2 solution through a syringe to a freshly prepared solution of 0.1 M SmI2 (1.0 mmol, 10 ml).</li>
 <li>Separately in a clean, dry vial under argon, add iodododecane (0.45 mmol, 110 &mu;l), 3-pentanone (0.45 mmol, 48 &mu;l) and 2 ml of dried THF.</li>
 <li>Add the substrate solution dropwise to the SmI2/Ni mixture.</li>
 <li>Within fifteen minutes of stirring, the blue color will dissipate to form a yellow-green color indicating the end of the reaction.</li>
 <li>After the reaction is complete, expose the solution to air to quench it; upon stirring the color further changes to yellow. Work up the reaction by washing with 0.1 M aq. Hydrochloric acid (3 ml). Add the solution to a separatory funnel and add diethylether (5 ml).</li>
 <li>Wash the organic layer using the protocol described previously with an aqueous solution of sodium thiosulfate, water and brine, and then dry over magnesium sulfate. Concentrate the solution to obtain Barbier product. The product can be identified by GCMS and 1H NMR.28</li>
</ol>

<ol>
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Soc. 122, 7718-7722 (2000).</li><li>Ito, Y., Takahashi, K., Nagase, H., Honda, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Integral+stereocontrolled+synthesis+of+a+spiro-norlignan,+sequosempervirin+A:+revision+of+absolute+configuration.">Integral stereocontrolled synthesis of a spiro-norlignan, sequosempervirin A: revision of absolute configuration.</a> Org. Lett. 13, 4640-4643 (2011).</li><li>Molander, G. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Toward+the+total+synthesis+of+Variecolin.">Toward the total synthesis of Variecolin.</a> Org. Lett. 3, 2257-2260 (2001).</li><li>Shabangi, M., Flowers, R. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electrochemical+investigation+of+the+reducing+power+of+SmI2+in+THF+and+the+effect+of+HMPA+cosolvent.">Electrochemical investigation of the reducing power of SmI2 in THF and the effect of HMPA cosolvent.</a> Tetrahedron Lett. 38, 1137-1140 (1997).</li><li>Enenaerke, R. J., Hertz, T., Skrydstrup, T., Daasbjerg, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Evidence+for+ionic+samarium(II)+species+in+THF/HMPA+solution+and+investigation+of+Their+electron-donating+properties.">Evidence for ionic samarium(II) species in THF/HMPA solution and investigation of Their electron-donating properties.</a> Chem. Eur. J. 6, 3747-3754 (2000).</li><li>Hou, Z., Zhang, Y., Wakatsuki, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Molecular+structures+of+HMPA-coordinated+samarium(II)+and+ytterbium(II)+iodide+complexes.+A+structural+basis+for+the+HMPA+effects+in+SmI2-promoted+reactions.">Molecular structures of HMPA-coordinated samarium(II) and ytterbium(II) iodide complexes. A structural basis for the HMPA effects in SmI2-promoted reactions.</a> Bull. Chem. Soc. Jpn. 70, 149-153 (1997).</li><li>Hou, Z., Wakatsuki, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=+Isolation+and+x-ray+structures+of+the+hexamethylphosphoramide+(hmpa)-coordinated+lanthanide(II)+diiodide+complexes+[SmI2(hmpa)4]+and+[Yb(hmpa)4(thf)2]I2."> Isolation and x-ray structures of the hexamethylphosphoramide (hmpa)-coordinated lanthanide(II) diiodide complexes [SmI2(hmpa)4] and [Yb(hmpa)4(thf)2]I2.</a> J. Chem. Soc., Chem Commun. 10, 1205-1206 (1994).</li><li>Sadasivam, D. V., Antharjanam, P. K. S., Prasad, E., Flowers, R. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanistic+study+of+samarium+diodide-HMPA+initiated+5-exo-trig+ketyl-Olefin+coupling:+the+role+of+HMPA+in+post-electron+transfer+steps.">Mechanistic study of samarium diodide-HMPA initiated 5-exo-trig ketyl-Olefin coupling: the role of HMPA in post-electron transfer steps.</a> J. Am. Chem. Soc. 130, 7228-7229 (2008).</li><li>Choquette, K. A., Sadasivam, D. V., Flowers, R. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Uncovering+the+mechanistic+role+of+HMPA+in+the+samarium+Barbier+reaction.">Uncovering the mechanistic role of HMPA in the samarium Barbier reaction.</a> J. Am. Chem. Soc. 132, 17396-17398 (2010).</li><li>Molander, G. A., Hu&#233;rou, V. L., Brown, G. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sequenced+reactions+with+samarium(II)+iodide.+Sequential+intramolecular+Barbier+byclization/Grob+fragmentation+for+the+synthesis+of+medium-sized+carbocycles.">Sequenced reactions with samarium(II) iodide. Sequential intramolecular Barbier byclization/Grob fragmentation for the synthesis of medium-sized carbocycles.</a> J. Org. Chem. 66, 4511-4516 (2001).</li><li>Molander, G. A., K&#246;llner, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Development+of+a+protocol+for+eight-+and+nine-membered+ring+synthesis+in+the+annulation+of+sp2,sp3-hybridized+organic+dihalides+with+keto+ester.">Development of a protocol for eight- and nine-membered ring synthesis in the annulation of sp2,sp3-hybridized organic dihalides with keto ester.</a> J. Org. Chem. 65, 8333-8339 (2000).</li><li>Molander, G. A., Alonso-Alija, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sequenced+reactions+with+samarium(II)+iodide.+Sequential+intermolecular+carbonyl+addition/intramolecular+nucleophilic+acyl+substitution+for+the+preparation+of+seven-,+eight-,+and+nine-membered+carbocycles.">Sequenced reactions with samarium(II) iodide. Sequential intermolecular carbonyl addition/intramolecular nucleophilic acyl substitution for the preparation of seven-, eight-, and nine-membered carbocycles.</a> J. Org. Chem. 63, 4366-4373 (1998).</li><li>Machrouhi, F., Hamann, B., Namy, J. L., Kagan, K. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Improved+reactivity+of+diiodosamarium+by+catalysis+with+transition+metal+salts.">Improved reactivity of diiodosamarium by catalysis with transition metal salts.</a> Synlett. 7, 633-634 (1996).</li><li>Choquette, K. A., Sadasivam, D. V., Flowers, R. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Catalytic+Ni(II)+in+reactions+of+SmI2:+Sm(II)-+or+Ni(0)-+based+chemistry?.">Catalytic Ni(II) in reactions of SmI2: Sm(II)- or Ni(0)- based chemistry?.</a> J. Am. Chem. Soc. 133, 10655-10661 (2011).</li></ol>

No conflicts of interest declared.

A straightforward procedure for generating SmI2 solution and its application in organic synthesis using two of the most common additives is presented here. The two examples described portray the importance of mechanistic understanding of the reaction to fine tune the reactivity of SmI2. Knowledge of the underpinning of the reaction mechanism allows the use of this reagent to be adapted by synthetic chemists as per the requirements of their reaction.
This single electron homogeneous reductant is easy to handle and can be purchased from commercial sources. While the above protocol is straight forward when done under inert conditions, some of the common troubleshooting procedures are: (a) make sure the THF is properly degassed and dry, (b) if Sm metal has had prolonged exposure to air it could have an oxidized outside layer, grind the metal with a mortar and pestal to expose the clean metal surface, (c) flame-dry all glassware and cool under argon, (d) argon is preferred inert atmosphere over Nitrogen, as the later has been shown to interact with the metal, (e) The presence of excess Sm-metal helps to maintain the concentration of SmI2, (f) resublime the iodine crystals.

<table border="1">
 <tbody>
 <tr>
 <td>Name of the reagent</td>
 <td>Company</td>
 <td>Catalogue number</td>
 <td>Comments (optional)</td>
 </tr>
 <tr>
 <td>Samarium metal</td>
 <td>Acros</td>
 <td>29478-0100</td>
 <td>-40 mesh, 99.9% (metals basis)</td>
 </tr>
 <tr>
 <td>THF</td>
 <td>OmniSolv</td>
 <td>TX0282-1</td>
 <td>Purified through Innovative Technologies solvent purification system. Alternatively it can be degassed through free-pump-thaw method</td>
 </tr>
 <tr>
 <td>Iodine</td>
 <td>Alfa Aesar</td>
 <td>41955-22</td>
 <td>Resublimed crystals, 99.8%</td>
 </tr>
 <tr>
 <td>Iodododecane</td>
 <td>Acros</td>
 <td>25009-0250</td>
 <td>98%</td>
 </tr>
 <tr>
 <td>3-pentanone</td>
 <td>Alfa Aesar</td>
 <td>AAA15297-AE</td>
 <td>99%</td>
 </tr>
 <tr>
 <td>HMPA</td>
 <td>Alderich</td>
 <td>H11602</td>
 <td>98%; distill from CaO under Argon</td>
 </tr>
 <tr>
 <td>NiI2</td>
 <td>Alfa Aesar</td>
 <td>22893</td>
 <td>99.5% (metals basis)</td>
 </tr>
 </tbody>
</table>

preparation and use of samarium diiodide (smi2) in organic synthesis: the mechanistic role of hmpa and ni(ii) salts in the samarium barbier reaction

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of molecular iodine to samarium metal in THF.1,2-3 It is a mild and selective single electron reductant and its versatility is a result of its ability to initiate a wide range of reductions including C-C bond-forming and cascade or sequential reactions. SmI2 can reduce a variety of functional groups including sulfoxides and sulfones, phosphine oxides, epoxides, alkyl and aryl halides, carbonyls, and conjugated double bonds.2-12 One of the fascinating features of SmI-2-mediated reactions is the ability to manipulate the outcome of reactions through the selective use of cosolvents or additives. In most instances, additives are essential in controlling the rate of reduction and the chemo- or stereoselectivity of reactions.13-14 Additives commonly utilized to fine tune the reactivity of SmI2 can be classified into three major groups: (1) Lewis bases (HMPA, other electron-donor ligands, chelating ethers, etc.), (2) proton sources (alcohols, water etc.), and (3) inorganic additives (Ni(acac)2, FeCl3, etc).3
Understanding the mechanism of SmI2 reactions and the role of the additives enables utilization of the full potential of the reagent in organic synthesis. The Sm-Barbier reaction is chosen to illustrate the synthetic importance and mechanistic role of two common additives: HMPA and Ni(II) in this reaction. The Sm-Barbier reaction is similar to the traditional Grignard reaction with the only difference being that the alkyl halide, carbonyl, and Sm reductant are mixed simultaneously in one pot.1,15 Examples of Sm-mediated Barbier reactions with a range of coupling partners have been reported,1,3,7,10,12 and have been utilized in key steps of the synthesis of large natural products.16,17 Previous studies on the effect of additives on SmI2 reactions have shown that HMPA enhances the reduction potential of SmI2 by coordinating to the samarium metal center, producing a more powerful,13-14,18 sterically encumbered reductant19-21 and in some cases playing an integral role in post electron-transfer steps facilitating subsequent bond-forming events.22 In the Sm-Barbier reaction, HMPA has been shown to additionally activate the alkyl halide by forming a complex in a pre-equilibrium step.23
Ni(II) salts are a catalytic additive used frequently in Sm-mediated transformations.24-27 Though critical for success, the mechanistic role of Ni(II) was not known in these reactions. Recently it has been shown that SmI2 reduces Ni(II) to Ni(0), and the reaction is then carried out through organometallic Ni(0) chemistry.28
These mechanistic studies highlight that although the same Barbier product is obtained, the use of different additives in the SmI2 reaction drastically alters the mechanistic pathway of the reaction. The protocol for running these SmI2-initiated reactions is described.

Figure 1 illustrates the samarium Barbier reaction. With no additives the Sm-mediated reaction takes 72 hr; yielding 69% of the desired product with the remaining being starting materials. With the addition of 10 or more equiv. of HMPA the reaction is nearly quantitative and complete within a few minutes.15,23 With the addition of 1 mol% Ni(acac)2, the reaction is complete within 15 min, with a 97% yield.28
When HMPA is added to SmI2, the cosolvent displaces the coordinated THF to form SmI2-(HMPA)4. With the addition of even more HMPA (6-10 equiv.), the iodide ions are displaced to the outer sphere (Figure 2).19-21 Mechanistic studies indicate that when HMPA is used in the Sm-Barbier reaction the cosolvent also interacts with the alkyl halide substrate forming a complex which elongates the carbon-halide bond, activating the species making it more susceptible to reduction by Sm (Figure 3). Through this detailed understanding of the roles of HMPA, a mechanism for the Sm-Barbier reaction with HMPA was proposed (Figure 4).23 The alkyl halide-HMPA complex formed in a pre-equilibrium step is reduced by Sm/HMPA to form the radical in the rate determining step. The radical undergoes further reduction to form an organosamarium species which couples with the carbonyl and upon protonation yields the final product.
In the case of Ni(II) additive, SmI2 initially reduces Ni(II) to Ni(0) preferentially over reduction of either of the substrates. Based on kinetic and mechanistic studies the following mechanism was proposed (Figure 5).28 After reduction by SmI2, the soluble Ni(0) species inserts into the alkyl halide bond forming an organonickel species. Driven by the highly oxophilic nature of Sm(III), transmetallation to form an organosamarium intermediate releases Ni(II) back into the catalytic cycle. The organosamarium then couples with the carbonyl, and upon protonation forms the desired tertiary alcohol. It was also observed that Ni(0) nanoparticles are formed through Sm-mediated reduction of Ni(II), however these particles were found to be inactive and the source of deactivation of the catalyst.
<img alt="Figure 1" fo:content-width="4in" fo:src="/files/ftp_upload/4323/4323fig1highres.jpg" src="/files/ftp_upload/4323/4323fig1.jpg" /> 
Figure 1. Samarium Barbier reaction with iodododecane and 3-pentanone.
<img alt="Figure 2" fo:content-width="4in" fo:src="/files/ftp_upload/4323/4323fig2highres.jpg" src="/files/ftp_upload/4323/4323fig2.jpg" /> 
Figure 2. SmI2-HMPA complex.
<img alt="Figure 3" fo:content-width="3.5in" fo:src="/files/ftp_upload/4323/4323fig3highres.jpg" src="/files/ftp_upload/4323/4323fig3.jpg" /> 
Figure 3. HMPA and alkyl iodide complex.
<img alt="Figure 4" fo:content-width="4.5in" fo:src="/files/ftp_upload/4323/4323fig4highres.jpg" src="/files/ftp_upload/4323/4323fig4.jpg" /> 
Figure 4. Proposed mechanism for the samarium Barbier reaction with excess HMPA.
<img alt="Figure 5" fo:content-width="4in" fo:src="/files/ftp_upload/4323/4323fig5highres.jpg" src="/files/ftp_upload/4323/4323fig5.jpg" /> 
Figure 5. Proposed mechanism for the samarium Barbier reaction containing catalytic Ni(II).

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Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction

A straightforward procedure for the preparation of samarium diiodide (SmI2) in THF is described. The role of two main additives namely hexamethylphosphoramide (HMPA) and Ni(acac)2 in Sm mediated reactions is demonstrated in the Sm-Barbier reaction.

Preparation and Use of Samarium Diiodide (SmI2) in Organic Synthesis: The Mechanistic Role of HMPA and Ni(II) Salts in the Samarium Barbier Reaction

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of ...

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32.5K vues.  Lehigh University. Un procédé simple pour la préparation de samarium diiodure (SMI 2) Dans du THF est décrit. Le rôle des deux principaux additifs savoir hexaméthylphosphoramide (HMPA) et Ni (acac) 2 Sm dans les réactions à médiation se manifeste dans la réaction Sm-Barbier.

Vidéo: Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction

A straightforward procedure for the preparation of samarium diiodide (SmI2) in THF is described. The role of two main additives namely hexamethylphosphoramide (HMPA) and Ni(acac)2 in Sm mediated reactions is demonstrated in the Sm-Barbier...

millifluidics for chemical synthesis and time-resolved mechanistic studies

Millifluidics for Chemical Synthesis and Time-resolved Mechanistic Studies

Millifluidic devices are utilized for controlled synthesis of nanomaterials, time-resolved analysis of reaction mechanisms and continuous flow...

metal-free synthesis of ynones from acyl chlorides and potassium alkynyltrifluoroborate salts

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

The goal of this manuscript is to demonstrate a straightforward method for the preparation of ynones from acyl chloride and potassium alkynyltrifluoroborate salt starting materials. The one-pot reaction proceeds rapidly in the presence of boron trichloride without exclusion of air and...

preparation and use of carbonyl-decorated carbenes in the activation of white phosphorus

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus

Here, we present a protocol for the synthesis of two carbonyl-decorated carbenes. The protocol makes these interesting compounds readily available to chemists of all skill levels. In addition to the synthesis of these two carbenes, their use in the activation of white phosphorus is also...

synthesis and characterization of functionalized metal-organic frameworks

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these...

effect of microwave synthesis conditions on the structure of nickel hydroxide nanosheets

Author Spotlight: A Rapid, Microwave-Assisted Hydrothermal Synthesis Of Nickel Hydroxide Nanosheets 

Nickel hydroxide nanosheets are synthesized by a microwave-assisted hydrothermal reaction. This protocol demonstrates that the reaction temperature and time used for microwave synthesis affects the reaction yield, crystal structure, and local coordination...

Microwave Synthesis and Characterization of Nickel Hydroxide Nanosheets

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synthesis and reaction chemistry of nanosize monosodium titanate

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

The surfactant mediated sol-gel synthesis of nanosized monosodium titanate is described, along with preparation of the corresponding peroxide modified material. An ion-exchange reaction with Au(III) is also...

thermochemical studies of ni(ii) and zn(ii) ternary complexes using ion mobility-mass spectrometry

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry

This article describes an experimental protocol using electrospray-ion mobility-mass spectrometry, semi-empirical quantum calculations, and energy-resolved threshold collision-induced dissociation to measure the relative thermochemistry of the dissociation of related ternary metal...

Thermochemical Studies of Ni(II) and Zn(II) Ternary Complexes Using Ion Mobility-Mass Spectrometry

preparation of expanded chitin foams and their use in the removal of aqueous copper

Preparation of Expanded Chitin Foams and their Use in the Removal of Aqueous Copper

This study describes a method to expand chitin into a foam by chemical techniques that require no specialized...

optimization of the ugi reaction using parallel synthesis and automated liquid handling

Optimization of the Ugi Reaction Using Parallel Synthesis and Automated Liquid Handling

The Ugi reaction has proved to be a convenient way to quickly create diverse libraries of compounds. It involves the reaction of an amine, an aldehyde, a carboxylic acid and an isonitrile typically in methanol at room temperature.   In this video,  we utilize a 48-slot Mettler-Toledo MiniBlock equipped with filtration tubes and a Mettler-Toledo MiniMapper automated liquid handler was used to deliver the reagents and solvent. The parameters of interest were the concentration, the solvent...

production and measurement of organic particulate matter in the harvard environmental chamber

Production and Measurement of Organic Particulate Matter in the Harvard Environmental Chamber

This paper describes operation procedures for the Harvard Environmental Chamber (HEC) and related instrumentation for measuring gaseous and particle species. The environmental chamber is used to produce and study secondary organic species produced from the organic precursors, especially related to atmospheric organic particulate matter.

visualization of twitching motility and characterization of the role of the pilg in xylella fastidiosa

Visualization of Twitching Motility and Characterization of the Role of the PilG in Xylella fastidiosa

In this study, a nano-microfluidic flow chamber was employed to visualize and functionally characterize the twitching motility of Xylella fastidiosa, a bacterium that causes Pierce&#39;s disease in...

Visualization of Twitching Motility and Characterization of the Role of the PilG in Xylella fastidiosa

microwave-assisted synthesis of &#945;-ni(oh)2 nanosheets

Microwave-Assisted Synthesis of &#945;-Ni(OH)2 Nanosheets  

Microwave-Assisted Synthesis of &#945;-Ni(OH)2 Nanosheets

modified technique for the use of neonatal murine hearts in the langendorff preparation

Modified Technique for the Use of Neonatal Murine Hearts in the Langendorff Preparation

The present protocol describes aortic cannulation and retrograde perfusion of the ex-vivo neonatal murine heart.  A two-person strategy, using a dissecting microscope and a blunted small gauge needle, permits reliable cannulation. Quantification of longitudinal contractile tension is achieved using a force transducer connected to the apex of the left...

experimental approaches for the synthesis of low-valent metal-organic frameworks from multitopic phosphine linkers

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers  

Here, we describe a protocol for the synthesis of low-valent metal-organic frameworks (LVMOFs) from low-valent metals and multitopic phosphine linkers under air-free conditions. The resulting materials have potential applications as heterogeneous catalyst mimics of low-valent metal-based homogeneous...

Synthesis of Low-Valent MOFs from Multitopic Phosphine Linkers

mechanistic insight into the development of tnbs-mediated intestinal fibrosis and evaluating the inhibitory effects of rapamycin

Mechanistic Insight into the Development of TNBS-Mediated Intestinal Fibrosis and Evaluating the Inhibitory Effects of Rapamycin

In this study, we describe a detailed procedure of TNBS-mediated intestinal fibrosis, which exhibits comparable pathophysiology to Crohn&#39;s fibrosis. We also discuss this approach in light of rapamycin facilitated inhibitory effects on intestinal...

palladium n-heterocyclic carbene complexes: synthesis from benzimidazolium salts and catalytic activity in carbon-carbon bond-forming reactions

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...

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

preparation of stable bicyclic aziridinium ions and their ring-opening for the synthesis of azaheterocycles

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles

Bicyclic aziridinium ions such as 1-azoniabicyclo[4.1.0]heptane tosylate were generated from 2-[4-tolenesulfonyloxybutyl]aziridine, which was utilized for the preparation of substituted piperidines and azepanes via regio- and stereospecific ring-expansion with various nucleophiles. This highly efficient protocol allowed us to prepare diverse azaheterocycles including natural products such as fagomine, febrifugine analogue and...

combining solid-state and solution-based techniques: synthesis and reactivity of chalcogenidoplumbates(ii or iv)

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV

The synthesis of chalcogenidoplumbates(II,IV) via the in situ reduction of nominal "PbCh2" (Ch = Chalcogen) and via a solid-state reaction and subsequent solvothermal reactions is presented. Additionally, reactivities of plumbate(II) solutions are portrayed, which yield the heaviest-known CO homolog known to date: the &#181;-PbSe ligand.

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

Synthesis, Cellular Delivery and In vivo Application of Dendrimer-based pH Sensors

The development of fluorescent indicators represented a revolution for life sciences. Genetically encoded and synthetic fluorophores with sensing abilities allowed the visualization of biologically relevant species with high spatial and temporal resolution. Synthetic dyes are of particular interest thanks to their high tunability and the wide range of measureable analytes. However, these molecules suffer several limitations related to small molecule behavior (poor solubility, difficulties in targeting, often no ratiometric imaging allowed). In this work we introduce the development of dendrimer-based sensors and present a procedure for pH measurement in vitro, in living cells and in vivo. We choose dendrimers as ideal platform for our sensors for their many desirable properties (monodispersity, tunable properties, multivalency) that made them a widely used scaffold for several biomedical devices. The conjugation of fluorescent pH indicators to the dendrimer scaffold led to an enhancement of their sensing performances. In particular dendrimers exhibit reduced cell leakage, improved intracellular targeting and allow ratiometric measurements. These novel sensors were successfully employed to measure pH in living HeLa cells and in vivo in mouse brain.

Synthesis, Cellular Delivery and In vivo Application of Dendrimer-based pH Sensors

Fluorescence sensors are powerful tools in life science. Here we describe a methodology to synthesize and use dendrimer-based fluorescent sensors to measure pH in living cells and in vivo. The dendritic scaffold enhances the properties of conjugated fluorescent dyes leading to improved sensing properties.

The development of  fluorescent indicators represented a revolution for life sciences. Genetically  encoded and synthetic fluorophores with sensing ...

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.

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

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

Here we present a protocol for the synthesis of two distinct carbonyl-decorated carbenes. Both carbenes can be prepared using nearly identical procedures in multi-gram scale quantities. The goal of this manuscript is to clearly detail how to handle and prepare these unique carbenes such that a synthetic chemist of any skill level can work with them. The two carbenes described are a diamidocarbene (DAC, carbene 1) and a monoamidoaminocarbene (MAAC 2). These carbenes are highly electron-deficient and as such display reactivity profiles that are atypical of more traditional N-heterocyclic carbenes. Additionally, these two carbenes only differ in their electrophilic character and not their steric parameters, making them ideal for studying how carbene electronics influence reactivity. To demonstrate this phenomenon, we are also describing the activation of white phosphorus (P4) using these carbenes. Depending on the carbene used, two very different phosphorus-containing compounds can be isolated. When the DAC 1 is used, a tris(phosphaalkenyl)phosphane can be isolated as the exclusive product. Remarkably however, when MAAC 2 is added to P4 under identical reaction conditions, an unexpected carbene-supported P8&#160;allotrope of phosphorus is isolated exclusively. Mechanistic studies demonstrate that this carbene-supported P8allotrope forms via a [2+2] cycloaddition dimerization of a transient diphosphene which has been trapped by treatment with 2,3-dimethyl-1,3-butadiene.

Here, we present a protocol for the synthesis of two carbonyl-decorated carbenes. The protocol makes these interesting compounds readily available to chemists of all skill levels. In addition to the synthesis of these two carbenes, their use in the activation of white phosphorus is also described.

Here we present a protocol for the synthesis of two distinct carbonyl-decorated carbenes. Both carbenes can be prepared using nearly identical procedures ...

Ynones are a valuable functional group and building block in organic synthesis. Ynones serve as a precursor to many important organic functional groups and scaffolds. Traditional methods for the preparation of ynones are associated with drawbacks including harsh conditions, multiple purification steps, and the presence of unwanted byproducts. An alternative method for the straightforward preparation of ynones from acyl chlorides and potassium alkynyltrifluoroborate salts is described herein. The adoption of organotrifluoroborate salts as an alternative to organometallic reagents for the formation of new carbon-carbon bonds has a number of advantages. Potassium organotrifluoroborate salts are shelf stable, have good functional group tolerance, low toxicity, and a wide variety are straightforward to prepare. The title reaction proceeds rapidly at ambient temperature in the presence of a Lewis acid without the exclusion of air and moisture. Fair to excellent yields may be obtained via reaction of various aryl and alkyl acid chlorides with alkynyltrifluoroborate salts in the presence of boron trichloride.

The goal of this manuscript is to demonstrate a straightforward method for the preparation of ynones from acyl chloride and potassium alkynyltrifluoroborate salt starting materials. The one-pot reaction proceeds rapidly in the presence of boron trichloride without exclusion of air and moisture.

Ynones are a valuable functional group and building block in organic synthesis. Ynones serve as a precursor to many important organic functional groups ...

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the material with Au(III) ions. The synthesis method was derived from a sol-gel process used to produce micron-sized monosodium titanate (MST), with several key modifications, including altering reagent concentrations, omitting a particle seed step, and introducing a non-ionic surfactant to facilitate control of particle formation and growth. The resultant nMST material exhibits spherical-shaped particle morphology with a monodisperse distribution of particle diameters in the range from 100 to 150&#160;nm. The nMST material was found to have a Brunauer-Emmett-Teller (BET) surface area of 285 m2g-1, which is more than an order of magnitude higher than the micron-sized MST. The isoelectric point of the nMST measured 3.34 pH units, which is a pH unit lower than that measured for the micron-size MST. The nMST material was found to serve as an effective ion exchanger under weakly acidic conditions for the preparation of an Au(III)-exchange nanotitanate. In addition, the formation of the corresponding peroxotitanate was demonstrated by reaction of the nMST with hydrogen peroxide.

The surfactant mediated sol-gel synthesis of nanosized monosodium titanate is described, along with preparation of the corresponding peroxide modified material. An ion-exchange reaction with Au(III) is also presented.

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the ...

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

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.

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

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single molecule level. An electrostatic self-assembly and covalent fixation (ESA-CF) process is used for the synthesis of the cyclic poly(tetrahydrofuran) (poly(THF)). The diffusive motion of individual cyclic polymer chains in a melt state is visualized using single molecule fluorescence imaging by incorporating a fluorophore unit in the cyclic chains. The diffusive motion of the chains is quantitatively characterized by means of a combination of mean-squared displacement (MSD) analysis and a cumulative distribution function (CDF) analysis. The cyclic polymer exhibits multiple-mode diffusion which is distinct from its linear counterpart. The results demonstrate that the diffusional heterogeneity of polymers that is often hidden behind ensemble averaging can be revealed by the efficient synthesis of the cyclic polymers using the ESA-CF process and the quantitative analysis of the diffusive motion at the single molecule level using the MSD and CDF analyses.

A protocol for the synthesis and characterization of diffusive motion of cyclic polymers at the single molecule level is presented.

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single ...

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.

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.

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