Why does thallium hydroxide increase the yield of product in a Suzuki reaction?Why does the Birch reaction not yield fully saturated products?How does cooling increase the selectivity of a reaction producing the kinetic vs the thermodynamic product?Why does neighbouring group participation increase the rate of reaction?The major product of the following reaction

What is the difference between "ещё" and "больше"?

How long should a hash be to be absolutely secure?

Why are adjacent breakers for unrelated circuits ganged?

Who's next to me in the queue?

Load extra fonts with lualatex

How do oases form in the middle of the desert?

Why does atmospheric pressure acts on us?

Can a Sorcerer use the Silence spell and the Subtle Spell Metamagic to silently cast the Knock spell?

Why do right-wing parties generally oppose the legalization of marijuana?

If you were to fly an ILS in a knife edge would you receve GS and LOC be fliped?

New manager unapproved PTO my old manager approved

Want to publish unpublished work found in an auction storage unit

What is written in this excerpt from a Manifest of Alien Passengers for the US arriving at Providence?

Why did they design new connectors for USB?

Why do we have to discharge the capacitor before testing it in an LCR Meter?

Merging 4 matrices to one matrix

How much tech advancement could be made out of modern processor appearing in 1980s?

If a picture of a screen is a screenshot, what is a video of a screen?

Why is the processor instruction called "move", not "copy"?

Is it OK for a Buddhist teacher to charge their students an hourly rate for their time?

C++ Leak detection simple class

Has there been clarification of the Random Weight Table in the Player's Handbook?

Is there any difference between 旅行者 and 旅人?

Does a patron have to know their warlock?



Why does thallium hydroxide increase the yield of product in a Suzuki reaction?


Why does the Birch reaction not yield fully saturated products?How does cooling increase the selectivity of a reaction producing the kinetic vs the thermodynamic product?Why does neighbouring group participation increase the rate of reaction?The major product of the following reaction






.everyoneloves__top-leaderboard:empty,.everyoneloves__mid-leaderboard:empty,.everyoneloves__bot-mid-leaderboard:empty
margin-bottom:0;









6















$begingroup$


I came across a research paper by Uenishi et al. [1] where relative rates of $ceKOH$ and $ceTlOH$ in Suzuki coupling reactions are compared.



Thallium hydroxide increased the yield of products, see Table I below. The reaction also occurred at room temperature as compared to $ceKOH$.
What is the effect of thallium hydroxide?




table summarizing the conditions of the reaction




References



  1. Uenishi, J.; Beau, J. M.; Armstrong, R. W.; Kishi, Y. Dramatic Rate Enhancement of Suzuki Diene Synthesis. Its Application to Palytoxin Synthesis. J. Am. Chem. Soc. 1987, 109 (15), 4756–4758. https://doi.org/10/fhmqsr.









share|improve this question











$endgroup$





















    6















    $begingroup$


    I came across a research paper by Uenishi et al. [1] where relative rates of $ceKOH$ and $ceTlOH$ in Suzuki coupling reactions are compared.



    Thallium hydroxide increased the yield of products, see Table I below. The reaction also occurred at room temperature as compared to $ceKOH$.
    What is the effect of thallium hydroxide?




    table summarizing the conditions of the reaction




    References



    1. Uenishi, J.; Beau, J. M.; Armstrong, R. W.; Kishi, Y. Dramatic Rate Enhancement of Suzuki Diene Synthesis. Its Application to Palytoxin Synthesis. J. Am. Chem. Soc. 1987, 109 (15), 4756–4758. https://doi.org/10/fhmqsr.









    share|improve this question











    $endgroup$

















      6













      6









      6


      1



      $begingroup$


      I came across a research paper by Uenishi et al. [1] where relative rates of $ceKOH$ and $ceTlOH$ in Suzuki coupling reactions are compared.



      Thallium hydroxide increased the yield of products, see Table I below. The reaction also occurred at room temperature as compared to $ceKOH$.
      What is the effect of thallium hydroxide?




      table summarizing the conditions of the reaction




      References



      1. Uenishi, J.; Beau, J. M.; Armstrong, R. W.; Kishi, Y. Dramatic Rate Enhancement of Suzuki Diene Synthesis. Its Application to Palytoxin Synthesis. J. Am. Chem. Soc. 1987, 109 (15), 4756–4758. https://doi.org/10/fhmqsr.









      share|improve this question











      $endgroup$




      I came across a research paper by Uenishi et al. [1] where relative rates of $ceKOH$ and $ceTlOH$ in Suzuki coupling reactions are compared.



      Thallium hydroxide increased the yield of products, see Table I below. The reaction also occurred at room temperature as compared to $ceKOH$.
      What is the effect of thallium hydroxide?




      table summarizing the conditions of the reaction




      References



      1. Uenishi, J.; Beau, J. M.; Armstrong, R. W.; Kishi, Y. Dramatic Rate Enhancement of Suzuki Diene Synthesis. Its Application to Palytoxin Synthesis. J. Am. Chem. Soc. 1987, 109 (15), 4756–4758. https://doi.org/10/fhmqsr.






      organic-chemistry reaction-mechanism experimental-chemistry






      share|improve this question















      share|improve this question













      share|improve this question




      share|improve this question








      edited Sep 28 at 13:50









      andselisk

      25.2k8 gold badges81 silver badges154 bronze badges




      25.2k8 gold badges81 silver badges154 bronze badges










      asked Sep 28 at 12:48









      ChemNomadChemNomad

      951 silver badge5 bronze badges




      951 silver badge5 bronze badges























          1 Answer
          1






          active

          oldest

          votes


















          5

















          $begingroup$

          The Suzuki coupling reaction (also called Suzuki-Miyaura coupling reactions; Ref.1) is the coupling of an aryl or vinyl boronic acid with an aryl or vinyl halide or triflate using a palladium(0) catalyst similar to Heck reaction and Negishi reactions in mechanistic aspects. In particular, Negishi reaction uses organozinc reagents instead of organoboronic acids. Both reactions are powerful cross-coupling methods that allows the synthesis of conjugated olefins, styrenes, and biphenyls. The mechanism of Suzuki coupling reaction is depicted below:



          Suzuki-Miyaura Reaction Mechanism



          The palladium catalyzed mechanism begins with oxidative addition of the organohalide ($ceR^1 -X$) to the $cePd(0)$ (e.g., $cePd(0)L_n$) to form a $cePd(II)$ complex (denoted in mechanism as $ceR^1 -Pd(II)L2X$). It is worth nothing that this first step in both of the Suzuki and Negishi cross-coupling reactions is identical to that of the Heck reaction. This complex undergoes halide ligand exchange with the base present in the reaction mixture.



          This base is present to serve one or two possible roles: Either to react with the organoboron reagent (denoted as $ceR^2 -B(OH)2$) to form a trialkoxyboronate (denoted as $ce^-B(OH)3R^2$), which then attacks the palladium(II) halide complex (denoted as $ceR^1 -Pd(II)L2X$), and/or to convert of the palladium(II) halide complex to a palladium(II) oxo complex (denoted as $ceR^1 -Pd(II)L2OH$) that reacts with the neutral organoboron reagent ($ceR^2 -B(OH)2$) (Ref.1 & 2).



          Transmetalation with the organoboron reagent then follows where the $ceR^2$ group of $ceR^2 -B(OH)2$ replaces the hydroxide anion on the palladium(II) complex to give $ceR^1R^2 -Pd(II)L2$ and boric acid. Keep in mind that organoboron compounds are highly covalent in character, and may not undergo transmetallation readily in the absence of a base. Therefore, the reaction of the base with the organoboron reagent, $ceR^2 -B(OH)2$ to form $ce^-B(OH)3R^2$ is very likely. Also note that transmetalation step is highly depend on the base availability and the types of ligand on the catalyst (Ref 1 & 3).



          Reductive elimination then follows to give the final coupled product regenerating the catalyst, hence the catalytic cycle can begin again.



          Based on this mechanism, availability of a base is very important to reaction to proceed. It is clear that AP's question does not indicate the solvent used in the reaction. However, mentioned reference has been using THF as the solvent. Since solubility of $ceKOH$ in THF is very low and hence its availability to the reaction. Thallium(I) hydroxide is strong base compatible with alkali bases such as $ceKOH$ and key to its capability of enhancing the reaction here should be its readily availability in such solvents. This is evidence that in recent publication (Ref.4) where $ceKOH$ and $ceTlOH$ are equally effective in $cePd(0)$ catalyzed coupling reaction, yield of which increases when solvent has been changed from THF to DMF.



          References:



          1. Norio Miyaura, Akira Suzuki, "Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds," Chem. Rev. 1995, 95(7), 2457-2483 (https://doi.org/10.1021/cr00039a007).

          2. Karl Matos, John A. Soderquist, "Alkylboranes in the Suzuki−Miyaura Coupling:  Stereochemical and Mechanistic Studies," J. Org. Chem. 1998, 63(3), 461-470 (https://doi.org/10.1021/jo971681s).

          3. Norio Miyaura, Kinji Yamada, Hiroshi Suginome, Akira Suzuki, "Novel and convenient method for the stereo- and regiospecific synthesis of conjugated alkadienes and alkenynes via the palladium-catalyzed cross-coupling reaction of 1-alkenylboranes with bromoalkenes and bromoalkynes," J. Am. Chem. Soc. 1985, 107(4), 972-980 (https://doi.org/10.1021/ja00290a037).

          4. Hiroko Koyama, Hisashi Doi, Masaaki Suzuki, "Evaluation of $ceTlOH$ Effect for $cePd^0$-Mediated Cross-Coupling of Methyl Iodide and Excess Boronic Acid Ester toward Fabrication of $ce[^11C]CH3$-Incorporated PET Tracer," Intl. J. Org. Chem. 2013, 3(3), 220-223 (DOI: 10.4236/ijoc.2013.33030).





          share|improve this answer










          $endgroup$









          • 1




            $begingroup$
            Toxicity of thallium hydroxide. pubchem.ncbi.nlm.nih.gov/compound/…
            $endgroup$
            – user55119
            Sep 29 at 2:46












          Your Answer








          StackExchange.ready(function()
          var channelOptions =
          tags: "".split(" "),
          id: "431"
          ;
          initTagRenderer("".split(" "), "".split(" "), channelOptions);

          StackExchange.using("externalEditor", function()
          // Have to fire editor after snippets, if snippets enabled
          if (StackExchange.settings.snippets.snippetsEnabled)
          StackExchange.using("snippets", function()
          createEditor();
          );

          else
          createEditor();

          );

          function createEditor()
          StackExchange.prepareEditor(
          heartbeatType: 'answer',
          autoActivateHeartbeat: false,
          convertImagesToLinks: false,
          noModals: true,
          showLowRepImageUploadWarning: true,
          reputationToPostImages: null,
          bindNavPrevention: true,
          postfix: "",
          imageUploader:
          brandingHtml: "Powered by u003ca class="icon-imgur-white" href="https://imgur.com/"u003eu003c/au003e",
          contentPolicyHtml: "User contributions licensed under u003ca href="https://creativecommons.org/licenses/by-sa/4.0/"u003ecc by-sa 4.0 with attribution requiredu003c/au003e u003ca href="https://stackoverflow.com/legal/content-policy"u003e(content policy)u003c/au003e",
          allowUrls: true
          ,
          onDemand: true,
          discardSelector: ".discard-answer"
          ,immediatelyShowMarkdownHelp:true
          );



          );














          draft saved

          draft discarded
















          StackExchange.ready(
          function ()
          StackExchange.openid.initPostLogin('.new-post-login', 'https%3a%2f%2fchemistry.stackexchange.com%2fquestions%2f121800%2fwhy-does-thallium-hydroxide-increase-the-yield-of-product-in-a-suzuki-reaction%23new-answer', 'question_page');

          );

          Post as a guest















          Required, but never shown


























          1 Answer
          1






          active

          oldest

          votes








          1 Answer
          1






          active

          oldest

          votes









          active

          oldest

          votes






          active

          oldest

          votes









          5

















          $begingroup$

          The Suzuki coupling reaction (also called Suzuki-Miyaura coupling reactions; Ref.1) is the coupling of an aryl or vinyl boronic acid with an aryl or vinyl halide or triflate using a palladium(0) catalyst similar to Heck reaction and Negishi reactions in mechanistic aspects. In particular, Negishi reaction uses organozinc reagents instead of organoboronic acids. Both reactions are powerful cross-coupling methods that allows the synthesis of conjugated olefins, styrenes, and biphenyls. The mechanism of Suzuki coupling reaction is depicted below:



          Suzuki-Miyaura Reaction Mechanism



          The palladium catalyzed mechanism begins with oxidative addition of the organohalide ($ceR^1 -X$) to the $cePd(0)$ (e.g., $cePd(0)L_n$) to form a $cePd(II)$ complex (denoted in mechanism as $ceR^1 -Pd(II)L2X$). It is worth nothing that this first step in both of the Suzuki and Negishi cross-coupling reactions is identical to that of the Heck reaction. This complex undergoes halide ligand exchange with the base present in the reaction mixture.



          This base is present to serve one or two possible roles: Either to react with the organoboron reagent (denoted as $ceR^2 -B(OH)2$) to form a trialkoxyboronate (denoted as $ce^-B(OH)3R^2$), which then attacks the palladium(II) halide complex (denoted as $ceR^1 -Pd(II)L2X$), and/or to convert of the palladium(II) halide complex to a palladium(II) oxo complex (denoted as $ceR^1 -Pd(II)L2OH$) that reacts with the neutral organoboron reagent ($ceR^2 -B(OH)2$) (Ref.1 & 2).



          Transmetalation with the organoboron reagent then follows where the $ceR^2$ group of $ceR^2 -B(OH)2$ replaces the hydroxide anion on the palladium(II) complex to give $ceR^1R^2 -Pd(II)L2$ and boric acid. Keep in mind that organoboron compounds are highly covalent in character, and may not undergo transmetallation readily in the absence of a base. Therefore, the reaction of the base with the organoboron reagent, $ceR^2 -B(OH)2$ to form $ce^-B(OH)3R^2$ is very likely. Also note that transmetalation step is highly depend on the base availability and the types of ligand on the catalyst (Ref 1 & 3).



          Reductive elimination then follows to give the final coupled product regenerating the catalyst, hence the catalytic cycle can begin again.



          Based on this mechanism, availability of a base is very important to reaction to proceed. It is clear that AP's question does not indicate the solvent used in the reaction. However, mentioned reference has been using THF as the solvent. Since solubility of $ceKOH$ in THF is very low and hence its availability to the reaction. Thallium(I) hydroxide is strong base compatible with alkali bases such as $ceKOH$ and key to its capability of enhancing the reaction here should be its readily availability in such solvents. This is evidence that in recent publication (Ref.4) where $ceKOH$ and $ceTlOH$ are equally effective in $cePd(0)$ catalyzed coupling reaction, yield of which increases when solvent has been changed from THF to DMF.



          References:



          1. Norio Miyaura, Akira Suzuki, "Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds," Chem. Rev. 1995, 95(7), 2457-2483 (https://doi.org/10.1021/cr00039a007).

          2. Karl Matos, John A. Soderquist, "Alkylboranes in the Suzuki−Miyaura Coupling:  Stereochemical and Mechanistic Studies," J. Org. Chem. 1998, 63(3), 461-470 (https://doi.org/10.1021/jo971681s).

          3. Norio Miyaura, Kinji Yamada, Hiroshi Suginome, Akira Suzuki, "Novel and convenient method for the stereo- and regiospecific synthesis of conjugated alkadienes and alkenynes via the palladium-catalyzed cross-coupling reaction of 1-alkenylboranes with bromoalkenes and bromoalkynes," J. Am. Chem. Soc. 1985, 107(4), 972-980 (https://doi.org/10.1021/ja00290a037).

          4. Hiroko Koyama, Hisashi Doi, Masaaki Suzuki, "Evaluation of $ceTlOH$ Effect for $cePd^0$-Mediated Cross-Coupling of Methyl Iodide and Excess Boronic Acid Ester toward Fabrication of $ce[^11C]CH3$-Incorporated PET Tracer," Intl. J. Org. Chem. 2013, 3(3), 220-223 (DOI: 10.4236/ijoc.2013.33030).





          share|improve this answer










          $endgroup$









          • 1




            $begingroup$
            Toxicity of thallium hydroxide. pubchem.ncbi.nlm.nih.gov/compound/…
            $endgroup$
            – user55119
            Sep 29 at 2:46















          5

















          $begingroup$

          The Suzuki coupling reaction (also called Suzuki-Miyaura coupling reactions; Ref.1) is the coupling of an aryl or vinyl boronic acid with an aryl or vinyl halide or triflate using a palladium(0) catalyst similar to Heck reaction and Negishi reactions in mechanistic aspects. In particular, Negishi reaction uses organozinc reagents instead of organoboronic acids. Both reactions are powerful cross-coupling methods that allows the synthesis of conjugated olefins, styrenes, and biphenyls. The mechanism of Suzuki coupling reaction is depicted below:



          Suzuki-Miyaura Reaction Mechanism



          The palladium catalyzed mechanism begins with oxidative addition of the organohalide ($ceR^1 -X$) to the $cePd(0)$ (e.g., $cePd(0)L_n$) to form a $cePd(II)$ complex (denoted in mechanism as $ceR^1 -Pd(II)L2X$). It is worth nothing that this first step in both of the Suzuki and Negishi cross-coupling reactions is identical to that of the Heck reaction. This complex undergoes halide ligand exchange with the base present in the reaction mixture.



          This base is present to serve one or two possible roles: Either to react with the organoboron reagent (denoted as $ceR^2 -B(OH)2$) to form a trialkoxyboronate (denoted as $ce^-B(OH)3R^2$), which then attacks the palladium(II) halide complex (denoted as $ceR^1 -Pd(II)L2X$), and/or to convert of the palladium(II) halide complex to a palladium(II) oxo complex (denoted as $ceR^1 -Pd(II)L2OH$) that reacts with the neutral organoboron reagent ($ceR^2 -B(OH)2$) (Ref.1 & 2).



          Transmetalation with the organoboron reagent then follows where the $ceR^2$ group of $ceR^2 -B(OH)2$ replaces the hydroxide anion on the palladium(II) complex to give $ceR^1R^2 -Pd(II)L2$ and boric acid. Keep in mind that organoboron compounds are highly covalent in character, and may not undergo transmetallation readily in the absence of a base. Therefore, the reaction of the base with the organoboron reagent, $ceR^2 -B(OH)2$ to form $ce^-B(OH)3R^2$ is very likely. Also note that transmetalation step is highly depend on the base availability and the types of ligand on the catalyst (Ref 1 & 3).



          Reductive elimination then follows to give the final coupled product regenerating the catalyst, hence the catalytic cycle can begin again.



          Based on this mechanism, availability of a base is very important to reaction to proceed. It is clear that AP's question does not indicate the solvent used in the reaction. However, mentioned reference has been using THF as the solvent. Since solubility of $ceKOH$ in THF is very low and hence its availability to the reaction. Thallium(I) hydroxide is strong base compatible with alkali bases such as $ceKOH$ and key to its capability of enhancing the reaction here should be its readily availability in such solvents. This is evidence that in recent publication (Ref.4) where $ceKOH$ and $ceTlOH$ are equally effective in $cePd(0)$ catalyzed coupling reaction, yield of which increases when solvent has been changed from THF to DMF.



          References:



          1. Norio Miyaura, Akira Suzuki, "Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds," Chem. Rev. 1995, 95(7), 2457-2483 (https://doi.org/10.1021/cr00039a007).

          2. Karl Matos, John A. Soderquist, "Alkylboranes in the Suzuki−Miyaura Coupling:  Stereochemical and Mechanistic Studies," J. Org. Chem. 1998, 63(3), 461-470 (https://doi.org/10.1021/jo971681s).

          3. Norio Miyaura, Kinji Yamada, Hiroshi Suginome, Akira Suzuki, "Novel and convenient method for the stereo- and regiospecific synthesis of conjugated alkadienes and alkenynes via the palladium-catalyzed cross-coupling reaction of 1-alkenylboranes with bromoalkenes and bromoalkynes," J. Am. Chem. Soc. 1985, 107(4), 972-980 (https://doi.org/10.1021/ja00290a037).

          4. Hiroko Koyama, Hisashi Doi, Masaaki Suzuki, "Evaluation of $ceTlOH$ Effect for $cePd^0$-Mediated Cross-Coupling of Methyl Iodide and Excess Boronic Acid Ester toward Fabrication of $ce[^11C]CH3$-Incorporated PET Tracer," Intl. J. Org. Chem. 2013, 3(3), 220-223 (DOI: 10.4236/ijoc.2013.33030).





          share|improve this answer










          $endgroup$









          • 1




            $begingroup$
            Toxicity of thallium hydroxide. pubchem.ncbi.nlm.nih.gov/compound/…
            $endgroup$
            – user55119
            Sep 29 at 2:46













          5















          5











          5







          $begingroup$

          The Suzuki coupling reaction (also called Suzuki-Miyaura coupling reactions; Ref.1) is the coupling of an aryl or vinyl boronic acid with an aryl or vinyl halide or triflate using a palladium(0) catalyst similar to Heck reaction and Negishi reactions in mechanistic aspects. In particular, Negishi reaction uses organozinc reagents instead of organoboronic acids. Both reactions are powerful cross-coupling methods that allows the synthesis of conjugated olefins, styrenes, and biphenyls. The mechanism of Suzuki coupling reaction is depicted below:



          Suzuki-Miyaura Reaction Mechanism



          The palladium catalyzed mechanism begins with oxidative addition of the organohalide ($ceR^1 -X$) to the $cePd(0)$ (e.g., $cePd(0)L_n$) to form a $cePd(II)$ complex (denoted in mechanism as $ceR^1 -Pd(II)L2X$). It is worth nothing that this first step in both of the Suzuki and Negishi cross-coupling reactions is identical to that of the Heck reaction. This complex undergoes halide ligand exchange with the base present in the reaction mixture.



          This base is present to serve one or two possible roles: Either to react with the organoboron reagent (denoted as $ceR^2 -B(OH)2$) to form a trialkoxyboronate (denoted as $ce^-B(OH)3R^2$), which then attacks the palladium(II) halide complex (denoted as $ceR^1 -Pd(II)L2X$), and/or to convert of the palladium(II) halide complex to a palladium(II) oxo complex (denoted as $ceR^1 -Pd(II)L2OH$) that reacts with the neutral organoboron reagent ($ceR^2 -B(OH)2$) (Ref.1 & 2).



          Transmetalation with the organoboron reagent then follows where the $ceR^2$ group of $ceR^2 -B(OH)2$ replaces the hydroxide anion on the palladium(II) complex to give $ceR^1R^2 -Pd(II)L2$ and boric acid. Keep in mind that organoboron compounds are highly covalent in character, and may not undergo transmetallation readily in the absence of a base. Therefore, the reaction of the base with the organoboron reagent, $ceR^2 -B(OH)2$ to form $ce^-B(OH)3R^2$ is very likely. Also note that transmetalation step is highly depend on the base availability and the types of ligand on the catalyst (Ref 1 & 3).



          Reductive elimination then follows to give the final coupled product regenerating the catalyst, hence the catalytic cycle can begin again.



          Based on this mechanism, availability of a base is very important to reaction to proceed. It is clear that AP's question does not indicate the solvent used in the reaction. However, mentioned reference has been using THF as the solvent. Since solubility of $ceKOH$ in THF is very low and hence its availability to the reaction. Thallium(I) hydroxide is strong base compatible with alkali bases such as $ceKOH$ and key to its capability of enhancing the reaction here should be its readily availability in such solvents. This is evidence that in recent publication (Ref.4) where $ceKOH$ and $ceTlOH$ are equally effective in $cePd(0)$ catalyzed coupling reaction, yield of which increases when solvent has been changed from THF to DMF.



          References:



          1. Norio Miyaura, Akira Suzuki, "Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds," Chem. Rev. 1995, 95(7), 2457-2483 (https://doi.org/10.1021/cr00039a007).

          2. Karl Matos, John A. Soderquist, "Alkylboranes in the Suzuki−Miyaura Coupling:  Stereochemical and Mechanistic Studies," J. Org. Chem. 1998, 63(3), 461-470 (https://doi.org/10.1021/jo971681s).

          3. Norio Miyaura, Kinji Yamada, Hiroshi Suginome, Akira Suzuki, "Novel and convenient method for the stereo- and regiospecific synthesis of conjugated alkadienes and alkenynes via the palladium-catalyzed cross-coupling reaction of 1-alkenylboranes with bromoalkenes and bromoalkynes," J. Am. Chem. Soc. 1985, 107(4), 972-980 (https://doi.org/10.1021/ja00290a037).

          4. Hiroko Koyama, Hisashi Doi, Masaaki Suzuki, "Evaluation of $ceTlOH$ Effect for $cePd^0$-Mediated Cross-Coupling of Methyl Iodide and Excess Boronic Acid Ester toward Fabrication of $ce[^11C]CH3$-Incorporated PET Tracer," Intl. J. Org. Chem. 2013, 3(3), 220-223 (DOI: 10.4236/ijoc.2013.33030).





          share|improve this answer










          $endgroup$



          The Suzuki coupling reaction (also called Suzuki-Miyaura coupling reactions; Ref.1) is the coupling of an aryl or vinyl boronic acid with an aryl or vinyl halide or triflate using a palladium(0) catalyst similar to Heck reaction and Negishi reactions in mechanistic aspects. In particular, Negishi reaction uses organozinc reagents instead of organoboronic acids. Both reactions are powerful cross-coupling methods that allows the synthesis of conjugated olefins, styrenes, and biphenyls. The mechanism of Suzuki coupling reaction is depicted below:



          Suzuki-Miyaura Reaction Mechanism



          The palladium catalyzed mechanism begins with oxidative addition of the organohalide ($ceR^1 -X$) to the $cePd(0)$ (e.g., $cePd(0)L_n$) to form a $cePd(II)$ complex (denoted in mechanism as $ceR^1 -Pd(II)L2X$). It is worth nothing that this first step in both of the Suzuki and Negishi cross-coupling reactions is identical to that of the Heck reaction. This complex undergoes halide ligand exchange with the base present in the reaction mixture.



          This base is present to serve one or two possible roles: Either to react with the organoboron reagent (denoted as $ceR^2 -B(OH)2$) to form a trialkoxyboronate (denoted as $ce^-B(OH)3R^2$), which then attacks the palladium(II) halide complex (denoted as $ceR^1 -Pd(II)L2X$), and/or to convert of the palladium(II) halide complex to a palladium(II) oxo complex (denoted as $ceR^1 -Pd(II)L2OH$) that reacts with the neutral organoboron reagent ($ceR^2 -B(OH)2$) (Ref.1 & 2).



          Transmetalation with the organoboron reagent then follows where the $ceR^2$ group of $ceR^2 -B(OH)2$ replaces the hydroxide anion on the palladium(II) complex to give $ceR^1R^2 -Pd(II)L2$ and boric acid. Keep in mind that organoboron compounds are highly covalent in character, and may not undergo transmetallation readily in the absence of a base. Therefore, the reaction of the base with the organoboron reagent, $ceR^2 -B(OH)2$ to form $ce^-B(OH)3R^2$ is very likely. Also note that transmetalation step is highly depend on the base availability and the types of ligand on the catalyst (Ref 1 & 3).



          Reductive elimination then follows to give the final coupled product regenerating the catalyst, hence the catalytic cycle can begin again.



          Based on this mechanism, availability of a base is very important to reaction to proceed. It is clear that AP's question does not indicate the solvent used in the reaction. However, mentioned reference has been using THF as the solvent. Since solubility of $ceKOH$ in THF is very low and hence its availability to the reaction. Thallium(I) hydroxide is strong base compatible with alkali bases such as $ceKOH$ and key to its capability of enhancing the reaction here should be its readily availability in such solvents. This is evidence that in recent publication (Ref.4) where $ceKOH$ and $ceTlOH$ are equally effective in $cePd(0)$ catalyzed coupling reaction, yield of which increases when solvent has been changed from THF to DMF.



          References:



          1. Norio Miyaura, Akira Suzuki, "Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds," Chem. Rev. 1995, 95(7), 2457-2483 (https://doi.org/10.1021/cr00039a007).

          2. Karl Matos, John A. Soderquist, "Alkylboranes in the Suzuki−Miyaura Coupling:  Stereochemical and Mechanistic Studies," J. Org. Chem. 1998, 63(3), 461-470 (https://doi.org/10.1021/jo971681s).

          3. Norio Miyaura, Kinji Yamada, Hiroshi Suginome, Akira Suzuki, "Novel and convenient method for the stereo- and regiospecific synthesis of conjugated alkadienes and alkenynes via the palladium-catalyzed cross-coupling reaction of 1-alkenylboranes with bromoalkenes and bromoalkynes," J. Am. Chem. Soc. 1985, 107(4), 972-980 (https://doi.org/10.1021/ja00290a037).

          4. Hiroko Koyama, Hisashi Doi, Masaaki Suzuki, "Evaluation of $ceTlOH$ Effect for $cePd^0$-Mediated Cross-Coupling of Methyl Iodide and Excess Boronic Acid Ester toward Fabrication of $ce[^11C]CH3$-Incorporated PET Tracer," Intl. J. Org. Chem. 2013, 3(3), 220-223 (DOI: 10.4236/ijoc.2013.33030).






          share|improve this answer













          share|improve this answer




          share|improve this answer










          answered Sep 28 at 17:46









          Mathew MahindaratneMathew Mahindaratne

          12.7k3 gold badges18 silver badges42 bronze badges




          12.7k3 gold badges18 silver badges42 bronze badges










          • 1




            $begingroup$
            Toxicity of thallium hydroxide. pubchem.ncbi.nlm.nih.gov/compound/…
            $endgroup$
            – user55119
            Sep 29 at 2:46












          • 1




            $begingroup$
            Toxicity of thallium hydroxide. pubchem.ncbi.nlm.nih.gov/compound/…
            $endgroup$
            – user55119
            Sep 29 at 2:46







          1




          1




          $begingroup$
          Toxicity of thallium hydroxide. pubchem.ncbi.nlm.nih.gov/compound/…
          $endgroup$
          – user55119
          Sep 29 at 2:46




          $begingroup$
          Toxicity of thallium hydroxide. pubchem.ncbi.nlm.nih.gov/compound/…
          $endgroup$
          – user55119
          Sep 29 at 2:46


















          draft saved

          draft discarded















































          Thanks for contributing an answer to Chemistry Stack Exchange!


          • Please be sure to answer the question. Provide details and share your research!

          But avoid


          • Asking for help, clarification, or responding to other answers.

          • Making statements based on opinion; back them up with references or personal experience.

          Use MathJax to format equations. MathJax reference.


          To learn more, see our tips on writing great answers.




          draft saved


          draft discarded














          StackExchange.ready(
          function ()
          StackExchange.openid.initPostLogin('.new-post-login', 'https%3a%2f%2fchemistry.stackexchange.com%2fquestions%2f121800%2fwhy-does-thallium-hydroxide-increase-the-yield-of-product-in-a-suzuki-reaction%23new-answer', 'question_page');

          );

          Post as a guest















          Required, but never shown





















































          Required, but never shown














          Required, but never shown












          Required, but never shown







          Required, but never shown

































          Required, but never shown














          Required, but never shown












          Required, but never shown







          Required, but never shown









          Popular posts from this blog

          Tamil (spriik) Luke uk diar | Nawigatjuun

          Align equal signs while including text over equalitiesAMS align: left aligned text/math plus multicolumn alignmentMultiple alignmentsAligning equations in multiple placesNumbering and aligning an equation with multiple columnsHow to align one equation with another multline equationUsing \ in environments inside the begintabularxNumber equations and preserving alignment of equal signsHow can I align equations to the left and to the right?Double equation alignment problem within align enviromentAligned within align: Why are they right-aligned?

          Training a classifier when some of the features are unknownWhy does Gradient Boosting regression predict negative values when there are no negative y-values in my training set?How to improve an existing (trained) classifier?What is effect when I set up some self defined predisctor variables?Why Matlab neural network classification returns decimal values on prediction dataset?Fitting and transforming text data in training, testing, and validation setsHow to quantify the performance of the classifier (multi-class SVM) using the test data?How do I control for some patients providing multiple samples in my training data?Training and Test setTraining a convolutional neural network for image denoising in MatlabShouldn't an autoencoder with #(neurons in hidden layer) = #(neurons in input layer) be “perfect”?