{"id":11763,"date":"2018-09-03T06:00:41","date_gmt":"2018-09-03T10:00:41","guid":{"rendered":"https:\/\/www.masterorganicchemistry.com\/?p=11763"},"modified":"2025-09-23T19:32:00","modified_gmt":"2025-09-24T00:32:00","slug":"diels-alder-kinetic-thermodynamic-exo-endo","status":"publish","type":"post","link":"https:\/\/www.masterorganicchemistry.com\/2018\/09\/03\/diels-alder-kinetic-thermodynamic-exo-endo\/","title":{"rendered":"Diels-Alder Reaction: Kinetic and Thermodynamic Control"},"content":{"rendered":"<p><strong>Kinetic and Thermodynamic Control In The Diels-Alder Reaction: The Diels Alder Reaction Is Reversible At High Temperatures<\/strong><\/p>\n<ul>\n<li>We&#8217;ve seen that the products of addition to dienes can be controlled using temperature (<span style=\"color: #993366;\"><em>See article &#8211; <a href=\"https:\/\/www.masterorganicchemistry.com\/2017\/03\/22\/reactions-of-dienes-12-and-14-addition\/\">Kinetic and Thermodynamic Control<\/a><\/em><\/span>).<\/li>\n<li>The Diels-Alder reaction is also subject to kinetic and thermodynamic control!<\/li>\n<li>At low temperatures the <em>endo<\/em> product dominates (<em><span style=\"color: #993366;\">the <strong>kinetic<\/strong> product, formed faster due to a lower-energy transition state &#8211; See article &#8211; <a style=\"color: #993366;\" href=\"https:\/\/www.masterorganicchemistry.com\/2018\/05\/11\/endo-vs-exo-in-the-diels-alder-reaction\/\">Why Do Diels-Alder Reactions Favor Endo Products?<\/a><\/span>)<\/em>.<\/li>\n<li>At higher temperatures, the Diels-Alder product is in <strong>equilibrium<\/strong> with its starting materials, and the product distribution is governed by the<strong> thermodynamic stability<\/strong> of the products.<\/li>\n<li>Since the\u00a0<em>exo <\/em>products tend to be less sterically hindered, they also tend to be the major products under conditions of\u00a0<strong>thermodynamic control<\/strong><\/li>\n<\/ul>\n<p><img fetchpriority=\"high\" decoding=\"async\" class=\"alignnone wp-image-34224\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2018\/09\/0-thermodynamic-vs-kinetic-products-in-the-Diels-Alder-reaction-cyclopentadiene-high-vs-low-energy-transition-states-2.gif\" alt=\"thermodynamic vs kinetic products in the Diels-Alder reaction cyclopentadiene high vs low energy transition states 2\" width=\"640\" height=\"650\" \/><\/a><\/p>\n<p><strong>Table of Contents<\/strong><\/p>\n<ol>\n<li><a href=\"#one\">The Commonly Used &#8220;Cyclopentadiene&#8221; Can&#8217;t Be Bought From Chemical Suppliers.\u00a0 Why?<\/a><\/li>\n<li><a href=\"#two\">Upon Standing For 1-2 Days At Room Temperature, Cyclopentadiene Slowly Undergoes Reaction To Give &#8220;Dicyclopentadiene&#8221;<\/a><\/li>\n<li><a href=\"#three\">Get Your Cyclopentadiene Back&#8230;\u00a0 With This &#8220;One Weird Trick&#8221;<\/a><\/li>\n<li><a href=\"#four\">Cyclopentadiene Slowly Undergoes A Diels-Alder Reaction With Itself To Give &#8220;Dicyclopentadiene&#8221;, Which Reverts Back To Cyclopentadiene Upon Heating To 180\u00b0C.<\/a><\/li>\n<li><a href=\"#five\">The Reverse (&#8220;Retro&#8221;) Diels-Alder Reaction: At High Temperatures, The Diels-Alder Reaction Is Reversible<\/a><\/li>\n<li><a href=\"#six\">Reaction Coordinate Diagram For The Diels-Alder Reaction<\/a><\/li>\n<li><a href=\"#seven\">Kinetic And Thermodynamic Control In The Diels-Alder<\/a><\/li>\n<li><a href=\"#eight\">A Reaction Coordinate Diagram For Kinetic vs. Thermodynamic Control In The Diels-Alder Reaction<\/a><\/li>\n<li><a href=\"#nine\">An <i>Exo<\/i>-Selective Diels-Alder Reaction<\/a><\/li>\n<li><a href=\"#ten\">More On The Retro Diels-Alder<\/a><\/li>\n<li><a href=\"#notes\">Notes<\/a><\/li>\n<li><a href=\"#quizzes\">Quiz Yourself!\u00a0<\/a><\/li>\n<li><a href=\"#references\">(Advanced) References and Further Reading<\/a><\/li>\n<\/ol>\n<hr \/>\n<h2><a id=\"one\"><\/a>1. The Commonly Used &#8220;Cyclopentadiene&#8221; Can&#8217;t Be Bought From Chemical Suppliers.\u00a0 Why?<\/h2>\n<p>Let&#8217;s talk about cyclopentadiene, a commonly used diene for Diels-Alder reactions that, by the way, comes up all the time on tests and exams. Like here:<\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-15711\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/1-cyclopentadiene-is-a-common-diene-used-in-diels-alder-reactions-eg-with-methyl-acrylate.gif\" alt=\"cyclopentadiene is a common diene used in diels alder reactions eg with methyl acrylate\" width=\"600\" height=\"206\" \/><\/p>\n<p>Gather around closely folks, because I&#8217;m going to tell you a little secret about this molecule. Something lots of people don&#8217;t know about. Something you&#8217;ll never believe.<\/p>\n<p>Despite the fact that you might see this being used in reactions all the time&#8230;<\/p>\n<p><strong>&#8230; you can&#8217;t actually <em>buy<\/em> cyclopentadiene!\u00a0<\/strong><\/p>\n<p>You heard that right.It&#8217;s not commercially available. Nobody on Earth sells the stuff. Call up Aldrich and ask for some. They&#8217;ll tell you that they don&#8217;t have any.<\/p>\n<p>In fact, <em>even if you do manage to get your hands on some<\/em>, if you leave it out on the bench for a day or so, <em>it goes away<\/em>! [<a href=\"#noteone\"><strong>Note 1<\/strong><\/a>]<\/p>\n<h2><a id=\"two\"><\/a>2. Upon Standing For 1-2 Days At Room Temperature, Cyclopentadiene Slowly Undergoes Reaction To Give &#8220;Dicyclopentadiene&#8221;<\/h2>\n<p>And by &#8220;goes away&#8221; I don&#8217;t mean that it evaporates&#8230; I mean that it <em>changes into a different molecule altogether.\u00a0<\/em><\/p>\n<p>The new molecule has a molecular formula of C<sub>10<\/sub>H<sub>12<\/sub> and has a completely different structure from cyclopentadiene.<\/p>\n<p>True fact!<\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-15712\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/2-cyclopentadiene-cannot-be-purchased-it-exists-as-a-dimer-dicyclopentadiene.gif\" alt=\"cyclopentadiene cannot be purchased it exists as a dimer dicyclopentadiene\" width=\"600\" height=\"249\" \/><\/p>\n<p>But check this out, folks. I&#8217;m about to tell you another little secret. A mind-blowing secret THEY don&#8217;t want you to know about.<\/p>\n<p>Introducing&#8230;<\/p>\n<h2><strong><a id=\"three\"><\/a>3. Get Your Cyclopentadiene Back&#8230;\u00a0 With This &#8220;One Weird Trick\u2122&#8221;<\/strong><\/h2>\n<p><em><del>Now only $19.95!<\/del> <strong>FREE! limited time offer!\u00a0<\/strong><\/em><\/p>\n<p>If you heat dicyclopentadiene to 180\u00b0C, and then distill it, you get your cyclopentadiene back!<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15713\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/3-heating-of-dicyclopentadiene-at-180-degrees-celsius-results-in-retro-diels-alder-to-give-cyclopetadiene-cracking.gif\" alt=\"heating of dicyclopentadiene at 180 degrees celsius results in retro diels alder to give cyclopetadiene cracking\" width=\"600\" height=\"277\" \/><\/p>\n<blockquote><p>&#8220;<strong>AMAZING!<\/strong>\u00a0I was skeptical, but this one weird trick totally worked! I&#8217;m so glad I got my cyclopentadiene back! Woohoo! &#8221;<\/p>\n<p>&#8211; <em>Homeau L&#8217;Oumeau, chemistry graduate student<\/em><\/p><\/blockquote>\n<hr \/>\n<h2><a id=\"four\"><\/a>4. Cyclopentadiene Slowly Undergoes A Diels-Alder Reaction With Itself To Give &#8220;Dicyclopentadiene&#8221;, Which Reverts Back To Cyclopentadiene Upon Heating To 180\u00b0C.<\/h2>\n<p>So what the heck is this &#8220;dicyclopentadiene&#8221; stuff, anyway? How does it form? And what happens when you heat it? How do you get cyclopentadiene back?<\/p>\n<p>As you may recall,\u00a0 cyclopentadiene is a particularly reactive diene, due to the fact that its double bond is locked in the &#8220;<em>s<\/em>-cis&#8221; conformation. [<span style=\"color: #993366;\"><em>See article: <a style=\"color: #993366;\" href=\"https:\/\/www.masterorganicchemistry.com\/2017\/05\/12\/s-cis-and-s-trans\/\">s-cis and s-trans\u00a0<\/a><\/em><\/span>]<\/p>\n<p>Cyclopentadiene that is left &#8220;neat&#8221; (i.e. undiluted) at room temperature [<a href=\"#noteone\">Note 1<\/a>]\u00a0 c<strong>an undergo a Diels-Alder reaction with itself<\/strong>, giving &#8220;dicyclopentadiene&#8221;. This is what our mysterious &#8220;dicyclopentadiene&#8221; looks like:<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/4-dicyclopentadiene-exists-as-mixture-of-endo-and-exo-products.gif\" alt=\"dicyclopentadiene exists as mixture of endo and exo products\" width=\"600\" height=\"200\" \/><\/p>\n<p>What about this &#8220;Diels-Alder reaction with itself&#8221; ?<\/p>\n<p>That means that one molecule of cyclopentadiene acts as a diene, and another molecule of cyclopentadiene acts as a dienophile.<\/p>\n<p>Here it is below, drawn in a way so that it looks just like all the previous Diels-Alder reactions we&#8217;ve shown in this series of posts.<\/p>\n<p>As usual, three pi bonds break, and two sigma bonds + one pi bond form:<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15715\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-at-room-temperature-cyclopentadiene-spontaneously-undergoes-diels-alder-reaction-with-itself.gif\" alt=\"at room temperature cyclopentadiene spontaneously undergoes diels alder reaction with itself\" width=\"600\" height=\"398\" \/><\/p>\n<p>As we&#8217;ve seen, the Diels-Alder can form both\u00a0<em>endo\u00a0<\/em>and\u00a0<em>exo<\/em> diastereomers [<span style=\"color: #993366;\"><em>See article<\/em>: <a style=\"color: #993366;\" href=\"https:\/\/www.masterorganicchemistry.com\/2018\/02\/09\/exo-vs-endo-products-in-the-diels-alder-how-to-tell-them-apart\/\"><em>Exo and Endo Products In The Diels-Alder &#8211; How To Tell them Apart\u00a0<\/em><\/a>]<\/span>.\u00a0 (only the\u00a0<em>endo<\/em> is shown here).<\/p>\n<p>Nothing new to see here, so far.<\/p>\n<p>Here&#8217;s the cool thing (and &#8211;\u00a0<em>shhhh! &#8211;\u00a0<\/em> the secret behind that &#8220;One Weird Trick&#8221; ). <strong>At high enough temperatures, the Diels-Alder reaction is reversible.<\/strong><\/p>\n<h2><strong><a id=\"five\"><\/a>5. The Reverse (&#8220;Retro&#8221;) Diels-Alder Reaction: At High Temperatures, The Diels-Alder Reaction Is Reversible<\/strong><\/h2>\n<p>That&#8217;s right. If you heat the product of a Diels-Alder reaction to a high enough temperature, the reaction can progress in <strong>reverse<\/strong>, regenerating the starting diene and dienophile (which both happen to be cyclopentadiene in this case).<\/p>\n<p>This is called the reverse (or &#8220;retro&#8221;) Diels-Alder reaction. In the &#8220;retro-Diels-Alder&#8221;:<\/p>\n<ul>\n<li>a six membered ring is broken,<\/li>\n<li>three C-C pi bonds are formed, and<\/li>\n<li>two single bonds + one pi bond are broken.<\/li>\n<\/ul>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15716\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/6-arrow-pushing-mechanism-of-the-reverse-retro-diels-alder-of-dicyclopentadiene-giving-cyclopentadiene.gif\" alt=\"arrow pushing mechanism of the reverse retro diels alder of dicyclopentadiene giving cyclopentadiene\" width=\"600\" height=\"256\" \/><\/p>\n<p>One consequence of this fact:<\/p>\n<p>Since the Diels-Alder is reversible at high temperature, this means that we should actually draw it as an equilibrium!<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15717\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/7-since-diels-alder-reaction-is-reversible-we-can-draw-it-as-an-equilibrium-that-lies-far-to-the-right-product-side.gif\" alt=\"since diels alder reaction is reversible we can draw it as an equilibrium that lies far to the right product side\" width=\"600\" height=\"233\" \/><\/p>\n<p><strong><em>Quiz.<\/em><\/strong> Why might high temperature favor the reverse reaction? Answer below [<a href=\"#notetwo\">Note 2<\/a>]<em>\u00a0[Hint: It has to do with\u00a0\u0394G =\u00a0\u0394H \u2013 T\u0394S]<\/em><\/p>\n<h2><a id=\"six\"><\/a>6. Reaction Coordinate Diagram For The Diels-Alder Reaction<\/h2>\n<p>A sketch of the reaction energy diagram for the Diels-Alder would look something like the the sketch below:<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15718\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/8-at-low-temperatures-diels-alder-reaction-is-irreversible-since-there-isnt-enough-energy-for-reverse-reaction-to-occur.gif\" alt=\"at low temperatures diels alder reaction is irreversible since there isnt enough energy for reverse reaction to occur\" width=\"630\" height=\"315\" \/><\/p>\n<p>Here we show\u00a0 \u0394E (blue) as the activation energy for the Diels Alder reaction in the forward direction, and a second \u0394E (in red) depicting the activation energy for the reverse reaction (with the <em>endo<\/em> depicted).<\/p>\n<p>At low temperatures, only the forward reaction is energetically accessible, but at higher temperatures,\u00a0 the reverse reaction can occur.<\/p>\n<p><strong>Why Should I Care?<\/strong><\/p>\n<p>You may very well ask why you need to care about this.<\/p>\n<p>Well, with a little more detail added, it will help us to solve at least one important lingering mystery. Helpfully, this also\u00a0<em>ties back to a concept we&#8217;ve already learned!\u00a0<\/em><\/p>\n<h2><strong><a id=\"seven\"><\/a>7. Kinetic And Thermodynamic Control In The Diels-Alder<\/strong><\/h2>\n<p>You may recall that the Diels-Alder tends to favor the <em>endo<\/em> product even though it would appear that the <em>exo<\/em> is in fact less sterically hindered (and, in addition, is more thermodynamically stable). This was puzzling at the time, and we had no good answer for it.\u00a0<em>[See: <a href=\"https:\/\/www.masterorganicchemistry.com\/2018\/05\/11\/why-are-endo-products-favored-in-the-diels-alder-reaction\/\">Why Are Endo Products Favored In The Diels-Alder?<\/a>]<\/em><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15719\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/9-endo-products-tend-to-be-favored-in-diels-alder-even-though-they-are-more-sterically-hindered-than-the-exo-products-.gif\" alt=\"endo products tend to be favored in diels alder even though they are more sterically hindered than the exo products\" width=\"630\" height=\"261\" \/><\/p>\n<p>In fact, it turns out to be another example of a concept covered earlier in this section on dienes, called <strong>Thermodynamic and Kinetic Control<\/strong> [<em>See: <a href=\"https:\/\/www.masterorganicchemistry.com\/2017\/03\/22\/reactions-of-dienes-12-and-14-addition\/\">Thermodynamic and Kinetic Control<\/a>]<\/em>.<\/p>\n<p>We saw examples of 1,2- versus 1,4 addition of HBr to dienes and wondered why it was that low temperatures favored the formation of the less stable product, whereas higher temperatures favored formation of the more stable product.<\/p>\n<p>We saw that at low temperatures (where the reaction is <em>irreversible<\/em>) products with the lowest-energy transition state\u00a0 were obtained [<strong>kinetic control<\/strong>]\u00a0 whereas in situations where the reaction was <em>reversible<\/em> (higher temperatures) the product mixture reflected the difference in heat of formation (i.e. energy) between the two products [<strong>thermodynamic control<\/strong>].<\/p>\n<p>The Diels-Alder presents us with another example of this very same phenomenon.<\/p>\n<h2><a id=\"eight\"><\/a>8. A Reaction Coordinate Diagram For Kinetic vs. Thermodynamic Control In The Diels-Alder Reaction<\/h2>\n<p>Let&#8217;s draw in the reaction coordinate for the\u00a0<em>exo<\/em> product (blue) to make it more clear.<\/p>\n<ul>\n<li>The transition state for the\u00a0<em>endo<\/em> product (C) is lower in energy than the transition state for the\u00a0<em>exo<\/em> product (B), meaning that it is\u00a0<em>formed faster (<\/em>i.e. has a lower activation energy)<\/li>\n<li>At low temperatures, the forward reaction to make the\u00a0<em>endo<\/em> is accessible (A\u2192C\u2192D) but not the reverse reaction (D\u2192C\u2192A). Therefore the reaction mixture will reflect the difference in energy between B and C. This is <strong>kinetic control.<\/strong><\/li>\n<li>At higher temperatures, the reverse reaction\u00a0(D\u2192C\u2192A) is energetically accessible, and the reaction becomes an equilibrium between starting materials (A) and the products (D and E). The reaction mixture will reflect the difference in energy of D and E. This is\u00a0<strong>thermodynamic control.\u00a0<\/strong><\/li>\n<\/ul>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15720\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/10-at-high-temperature-when-diels-alder-reversible-can-get-thermodynamic-control-in-diels-alder-reaction-exo-favored-over-endo.gif\" alt=\"at high temperature when diels alder reversible can get thermodynamic control in diels alder reaction exo favored over endo\" width=\"630\" height=\"597\" \/><\/p>\n<p>The Diels-Alder is normally run under conditions where the reaction is irreversible, and for reasons we discussed previously [in\u00a0<a href=\"https:\/\/www.masterorganicchemistry.com\/2018\/05\/11\/why-are-endo-products-favored-in-the-diels-alder-reaction\/\"><em>Why Are Endo Products Favored In The Diels-Alder<\/em><\/a>?] the\u00a0<em>endo\u00a0<\/em>transition state tends to be lower in energy than the\u00a0<em>exo\u00a0<\/em>transition state. Hence, <em>endo\u00a0<\/em>products tend to dominate at low temperatures.<\/p>\n<p>But at higher temperatures, where the reaction is reversible, more of the\u00a0<em>exo\u00a0<\/em>product will form due to its greater thermodynamic stability. For example, while the Diels-Alder of cyclopentadiene with itself at 23\u00b0C gives only the <em>endo<\/em> product,\u00a0heating a solution of cyclopentadiene at 200 \u00b0C\u00a0 over about 2 days gives an\u00a0<em>endo:exo\u00a0<\/em>ratio of 4:1. [<em><a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/jo00384a016?src=recsys&amp;journalCode=joceah\">source<\/a><\/em>]\u00a0 .<\/p>\n<p>One can even heat a pure\u00a0<em>endo<\/em> product and obtain a mixture of\u00a0<em>exo<\/em> and\u00a0<em>endo<\/em> products!<\/p>\n<h2><strong><a id=\"nine\"><\/a>9. An <em>Exo<\/em>-Selective Diels-Alder Reaction<\/strong><\/h2>\n<p>Here&#8217;s one prominent example of an\u00a0<em>exo<\/em>-selective Diels-Alder reaction.<\/p>\n<p>Furan (below) appears similar to cyclopentadiene. But as you may already have seen (<span style=\"color: #993366;\"><em>or will soon see, here<\/em>:\u00a0<\/span><em><span style=\"color: #993366;\"><a style=\"color: #993366;\" href=\"https:\/\/www.masterorganicchemistry.com\/2017\/02\/23\/rules-for-aromaticity\/\">Rules For Aromaticity<\/a><\/span>]\u00a0<\/em>furan has a peculiar property called\u00a0<strong>aromaticity<\/strong>: for this reason, it is about 20 kcal\/mol more stable than one would expect based on bond energies alone. Furan <em>can<\/em> act as a diene in Diels-Alder reactions, but this disrupts the aromaticity of furan. For this reason, Diels-Alder products of furan undergo retro Diels-Alder reactions at much lower temperatures than those of most other dienes.<\/p>\n<p>For example, the Diels-Alder reaction of furan with maleic anhydride in acetonitrile at 40 \u00b0C gives the\u00a0<em>exo<\/em> product exclusively after 48 h.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15721\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/11-diels-alder-reaction-of-furan-with-maleic-anhydride-is-highly-reversible-gives-exo-product-under-thermodynamic-control.gif\" alt=\"diels alder reaction of furan with maleic anhydride is highly reversible gives exo product under thermodynamic control\" width=\"600\" height=\"345\" \/><\/p>\n<p><span style=\"color: #993366;\"><em>[Interestingly, in this reaction the endo is intially the dominant product (formed at a rate about 500 times faster than the exo, [<a style=\"color: #993366;\" href=\"#notethree\">Note 3<\/a>], but quickly reverts to the starting materials. Owing to the difference of 1.9 kcal\/mol between the exo and endo products, the exo is the dominant product isolated. ]<\/em><\/span><\/p>\n<h2><a id=\"ten\"><\/a>10. More On The Retro Diels-Alder<\/h2>\n<p>This is probably enough for one post, but in the next one we&#8217;ll briefly go through a few prominent examples of retro Diels-Alder reactions and see how they can be applied in synthesis.<\/p>\n<p>Next post: <a href=\"https:\/\/www.masterorganicchemistry.com\/2018\/10\/01\/the-retro-diels-alder-reaction\/\">The Retro Diels-Alder Reaction<\/a><\/p>\n<hr \/>\n<h2><a id=\"notes\"><\/a>Notes<\/h2>\n<div class=\"related-articles\"><p><strong>Related Articles<\/strong><\/p><ul><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2018\/10\/01\/the-retro-diels-alder-reaction\/\" class=\"\"><span>The Retro Diels-Alder Reaction<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2017\/05\/12\/s-cis-and-s-trans\/\" class=\"\"><span>s-cis and s-trans<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/02\/09\/kinetic-thermodynamic-products-can-openers\/\" class=\"\"><span>Thermodynamic and Kinetic Products<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2017\/03\/22\/reactions-of-dienes-12-and-14-addition\/\" class=\"\"><span>Reactions of Dienes: 1,2 and 1,4 Addition<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2017\/04\/11\/more-on-12-and-14-additions-to-dienes\/\" class=\"\"><span>More On 1,2 and 1,4 Additions To Dienes<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2017\/08\/30\/the-diels-alder-reaction\/\" class=\"\"><span>The Diels-Alder Reaction<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/organic-chemistry-practice-problems\/diels-alder-practice-problems\/\" class=\"\"><span>Diels Alder Practice Problems (MOC Membership)<\/span><\/a><\/li><\/ul><\/div>\n<p><a id=\"notetwo\"><\/a><strong>Note 1<\/strong>. Although, it should be noted, cyclopentadiene can be kept in the freezer indefinitely.<\/p>\n<p><a id=\"noteone\"><\/a><strong>Note 2<\/strong>. Why might higher temperatures favor the reverse Diels-Alder?<\/p>\n<p>Recall that for any reaction to be &#8220;spontaneous&#8221; , the Gibbs free energy\u00a0\u0394G must be negative:<\/p>\n<p>\u0394G =\u00a0\u0394H \u2013 T\u0394S<\/p>\n<p>where\u00a0 \u0394S is the entropy.<\/p>\n<p>Even a reaction that is endothermic (positive\u00a0\u0394H) can be made to be spontaneous through heating if the reaction itself has a large entropy (\u0394S).<\/p>\n<p>[The heat of formation for the reaction between cyclopentadiene and maleic anhydride is about \u201325 kcal\/mol at room temperature, which would make the\u00a0\u0394H +25 kcal\/mol for the reverse reaction]. [<a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/jo00919a034?src=recsys\">Source<\/a>]<\/p>\n<p>In the retro Diels-Alder, a single molecule (the Diels-Alder product) reverts to two starting molecules (the diene and dienophile), which represents a large net increase in entropy. Therefore, heating the reaction (increasing T) will make the \u2013T\u0394S term increasingly negative, until it dominates the positive\u00a0\u0394H term.<\/p>\n<p><a id=\"notethree\"><\/a><strong>Note 3<\/strong>. The difference in rate of 500 gives a difference in activation energy of 3.8 kcal\/mol favoring the\u00a0<em>endo<\/em>.<\/p>\n<hr \/>\n<h2><a id=\"quizzes\"><\/a>Quiz Yourself!<\/h2>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3404-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3405-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3406-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <br \/>\n&nbsp;<\/p>\n<hr \/>\n<h2><a id=\"references\"><\/a>(Advanced) References and Further Reading<\/h2>\n<ol>\n<li><strong>FERROCENE<br \/>\n<\/strong>G. Wilkinson<strong><br \/>\n<\/strong><em>Org. Synth.<\/em><strong> 1956<\/strong>, <em>36<\/em>, 31<strong><br \/>\nDOI: <\/strong><a href=\"http:\/\/www.orgsyn.org\/demo.aspx?prep=CV4P0473\">10.15227\/orgsyn.036.0031<\/a><br \/>\nThe synthesis of ferrocene is commonly carried out in undergraduate labs today, and this requires cyclopentadiene, prepared by \u2018cracking\u2019 of dicyclopentadiene. This procedure is particularly famous, as the discovery of ferrocene kicked off the field of modern organometallic chemistry in the 20<sup>th<\/sup> century. Prof. Wilkinson went on to receive the Nobel Prize for his work in this regard.<\/li>\n<li><strong>Study of the Diels\u2013Alder and retro-Diels\u2013Alder reaction between furan derivatives and maleimide for the creation of new materials<\/strong><br \/>\nV. Froidevaux, M. Borne, E. Laborbe, R. Auvergne, A. Gandinib, and B. Boutevin<br \/>\n<em>RSC Adv.,<\/em> <strong>2015<\/strong>, <em>5<\/em>, 37742-37754<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/pubs.rsc.org\/en\/content\/articlelanding\/2015\/ra\/c5ra01185j#!divAbstract\">10.1039\/C5RA01185J<\/a><\/li>\n<li><strong>Synthetic applications of furan Diels-Alder chemistry<br \/>\n<\/strong> Oliver Kappe, S. Shaun Murphree, and Albert Padwa<br \/>\n<em>Tetrahedron<\/em> <strong>1997<\/strong>, <em>53<\/em> (42), 14179-14233<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/www.sciencedirect.com\/science\/article\/abs\/pii\/S0040402097007473\">10.1016\/S0040-4020(97)00747-3<\/a><br \/>\nThese two reviews cover the mechanistic aspects and synthetic applications of the Diels-Alder reaction with furan.<\/li>\n<li><strong>endo- and exo-Stereochemistry in the Diels-Alder Reaction: Kinetic versus Thermodynamic Control<br \/>\n<\/strong>James H. Cooley and Richard Vaughan Williams<br \/>\n<em>Journal of Chemical Education<\/em> <strong>1997,<\/strong> <em>74<\/em> (5), 582<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/ed074p582\">10.1021\/ed074p582<\/a><br \/>\nAn experiment suitable for undergraduates that illustrates thermodynamic and kinetic control in Diels-Alder reactions.<\/li>\n<li><strong>Thermodynamic vs. kinetic control in the Diels-Alder cycloaddition of cyclopentadiene to 2,3-dicyano-p-benzoquinone<\/strong><br \/>\nBott, S.G., Marchand, A.P. &amp; Kumar, K.A.<br \/>\n<em> Chem. Crystallogr.<\/em> <strong>1996<\/strong>, <em>26<\/em>, 281\u2013286<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/link.springer.com\/article\/10.1007\/BF01677782\">10.1007\/BF01677782<\/a><br \/>\nScheme 2 in this paper illustrates a representative Diels-Alder reaction that gives <em>endo<\/em> or <em>exo<\/em> products under thermodynamic or kinetic conditions, respectively, and that the kinetic (<em>exo<\/em>) product can be converted to the thermodynamic (<em>endo<\/em>) product upon heating.<\/li>\n<li><a href=\"https:\/\/organicchemistrydata.org\/hansreich\/resources\/pericyclic\/#pericyclic04\">https:\/\/organicchemistrydata.org\/hansreich\/resources\/pericyclic\/#pericyclic04<\/a><br \/>\nThe late Prof. Hans Reich (U. Wisconsin-Madison) had a website full of useful information on organic chemistry, including this page on the Diels-Alder reaction. His website is now being maintained by the ACS Division of Organic Chemistry.<\/li>\n<\/ol>\n","protected":false},"excerpt":{"rendered":"<p>Kinetic and Thermodynamic Control In The Diels-Alder Reaction: The Diels Alder Reaction Is Reversible At High Temperatures We&#8217;ve seen that the products of addition to <\/p>\n","protected":false},"author":1,"featured_media":34224,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_acf_changed":false,"footnotes":""},"categories":[1163],"tags":[1257,631,1249,1250,361,488,1357,362],"post_folder":[],"class_list":["post-11763","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-dienes-and-mo-theory","tag-cyclopentadiene","tag-diels-alder","tag-diene","tag-dienophile","tag-kinetic-control","tag-reaction-coordinate","tag-retro-diels-alder","tag-thermodynamic-control"],"acf":[],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.7 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Kinetic and Thermodynamic Control in the Diels-Alder Reaction<\/title>\n<meta name=\"description\" content=\"The Diels Alder reaction can be under kinetic or thermodynamic control. 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