{"id":8715,"date":"2015-02-02T13:38:32","date_gmt":"2015-02-02T18:38:32","guid":{"rendered":"https:\/\/www.masterorganicchemistry.com\/?p=8715"},"modified":"2025-03-06T09:40:20","modified_gmt":"2025-03-06T15:40:20","slug":"opening-of-epoxides-with-acid","status":"publish","type":"post","link":"https:\/\/www.masterorganicchemistry.com\/2015\/02\/02\/opening-of-epoxides-with-acid\/","title":{"rendered":"Opening of Epoxides With Acid"},"content":{"rendered":"<p><strong>Opening Epoxides With Aqueous Acid<\/strong><\/p>\n<ul>\n<li>Epoxides can undergo ring-opening with nucleophiles under acidic conditions.<\/li>\n<li>In this reaction, the epoxide oxygen is protonated first, making it a better leaving group<\/li>\n<li>In the second step, the nucleophile tends to attack the more substituted carbon, which breaks the weakest C-O bond.<\/li>\n<li>The best analogy is that it is a lot like the Markovnikov opening of bromonium or mercurinium ions.<\/li>\n<\/ul>\n<p><img fetchpriority=\"high\" decoding=\"async\" class=\"alignnone wp-image-15169\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/0-summary-opening-epoxides-under-acidic-conditions-occurs-in-two-steps-first-protonate-epoxide-second-nucleophile-attacks-most-substituted-position-backside-attack.gif\" alt=\"summary opening epoxides under acidic conditions occurs in two steps first protonate epoxide second nucleophile attacks most substituted position backside attack\" width=\"600\" height=\"298\" \/><\/p>\n<p><strong>Table of Contents<\/strong><\/p>\n<ol>\n<li><a href=\"#one\">Formation of\u00a0<em>trans<\/em>-Diols Through Opening of Epoxides With Aqueous Acid<\/a><\/li>\n<li><a href=\"#two\">The Mechanism For Opening of\u00a0<em>trans<\/em>-Diols With Acid Is Similar To Opening Halonium Ions<\/a><\/li>\n<li><a href=\"#three\">Other Nucleophiles: Alcohols and HX<\/a><\/li>\n<li><a href=\"#four\">Acid Only Helps The Reaction If The Nucleophile Is Compatible With Strong Acid<\/a><\/li>\n<li><a href=\"#five\">What About Opening of Epoxides With Base?<\/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><strong><a id=\"one\"><\/a>1. Formation of <em>trans-<\/em>Diols Through Opening of\u00a0 Epoxides With Aqueous Acid<\/strong><\/h2>\n<p>In the last post, we saw some examples of how epoxides are considerably more reactive towards breakage than are ordinary ethers. For example, aqueous acid [often abbreviated &#8220;H<sub>3<\/sub>O+&#8221;] will open an epoxide under MUCH milder conditions than an &#8220;ordinary&#8221; ether such as diethyl ether, because epoxides have considerable ring strain [about 13 kcal\/mol].<\/p>\n<p>Looking more closely at the reaction, we also noted two interesting patterns:<\/p>\n<ul>\n<li>the nucleophile attacks at the &#8220;more substituted&#8221; position of the epoxide (C-1, below)<\/li>\n<li>inversion of stereochemistry occurs at this position, but not at the other position (note that the C-O bond at C-2 below is a &#8220;wedge&#8221; in both starting material and product ).<\/li>\n<\/ul>\n<p><img decoding=\"async\" class=\"alignnone wp-image-15170\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/1-epoxides-react-with-aqueous-acid-to-produce-trans-diols-attack-at-most-substituted-position-of-epoxide.gif\" alt=\"epoxides react with aqueous acid to produce trans diols attack at most substituted position of epoxide\" width=\"600\" height=\"188\" \/><\/p>\n<p><em>[<span style=\"color: #993366;\">By the way, how do we &#8220;know&#8221; that the OH on C-1 is from the nucleophile and is not the epoxide? Using isotopic labels is one way. Another is to use nucleophiles other than water &#8211; see below]<\/span><\/em><\/p>\n<p>It should be noted that in the <strong>absence of acid, no reaction occurs<\/strong>. So clearly the \u00a0H+ plays a key role.<\/p>\n<p>What could be going on?<\/p>\n<p>By analogy to the reaction of ethers with acid, the first step must be reaction of the most basic site on the molecule &#8211; the epoxide oxygen &#8211; with acid, giving us a protonated epoxide. This will function as a much better leaving group than does the unprotonated epoxide.\u00a0 [<span style=\"color: #993366;\"><em>Recall that the <a style=\"color: #993366;\" href=\"https:\/\/www.masterorganicchemistry.com\/2011\/04\/12\/what-makes-a-good-leaving-group\/\">conjugate acid is always a better leaving group<\/a><\/em><\/span>]<\/p>\n<p>The next step must then be reaction of the best nucleophile present in solution &#8211; H<sub>2<\/sub>O, in this case &#8211; with our protonated epoxide. And this occurs at the most substituted position, always with inversion of stereochemistry. So it must be performing a &#8220;backside attack&#8221; at this carbon, as we observe in S<sub>N<\/sub>2 reactions. A final deprotonation gives us the neutral product.<\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-15171\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/2-mechanism-for-opening-epoxide-under-acidic-conditions-first-protonation-of-epoxide-second-attack-of-nucleophile-water-step-3-deprotonation.gif\" alt=\"mechanism for opening epoxide under acidic conditions first protonation of epoxide second attack of nucleophile water step 3 deprotonation\" width=\"630\" height=\"236\" \/><\/p>\n<p>Hold on for a second. If you remember the key lesson of the S<sub>N<\/sub>2\u00a0&#8211; that it is disfavoured by steric hindrance &#8211; this might seem weird. \u00a0If this was a &#8220;pure&#8221; S<sub>N<\/sub>2, reaction, wouldn&#8217;t we expect the attack to occur as the &#8220;least substituted&#8221; position?<\/p>\n<p>Clearly something else must be going on here!<\/p>\n<h2><a id=\"two\"><\/a>2. The Mechanism for Opening Epoxides With\u00a0 Acid Is Just Like Opening Halonium and Mercurinium Ions<\/h2>\n<p>Thankfully, you&#8217;ve likely encountered reactions like this before! \u00a0If you think back to the chapter on alkenes, you might see\u00a0that the protonated epoxide bears an uncanny resemblance to two other reactive intermediates you met in that chapter: &#8220;halonium&#8221; ions, and &#8220;mercurinium&#8221; ions, both 3-membered rings bearing a positive charge:<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15172\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/3-protonated-epoxides-very-similar-to-halonium-mercuriniium-ions-behave-the-same-way-3-membered-ring-pathway.gif\" alt=\"protonated epoxides very similar to halonium mercuriniium ions behave the same way 3 membered ring pathway\" width=\"600\" height=\"190\" \/><\/p>\n<p>If you think back to how these species reacted with nucleophiles, it was always at the\u00a0<strong>more substituted<\/strong> position with <strong>inversion<\/strong> of stereochemistry. In fact, there is a whole family of alkene addition reactions that proceed this mechanism that we called the &#8220;<a href=\"https:\/\/www.masterorganicchemistry.com\/2013\/03\/20\/alkene-addition-pattern-2-the-three-membered-ring-pathway\/\">3-membered ring pathway<\/a>&#8220;. Halohydrin formation is a perfect example:<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15173\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/4-recall-halohydrin-formation-addition-of-br2-water-to-alkenes-attack-at-most-substituted-carbon.gif\" alt=\"recall halohydrin formation addition of br2 water to alkenes attack at most substituted carbon\" width=\"630\" height=\"240\" \/><\/p>\n<p>So in essence, the addition of nucleophiles to protonated epoxides is just\u00a0another example of the &#8220;3 membered ring pathway&#8221; of alkenes!<\/p>\n<p>[<em><span style=\"color: #993366;\">Need a review on why the nucleophile attacks the most substituted carbon? See<\/span> <a href=\"#noteone\">Note 1<\/a>\u00a0and then come back<\/em>]<\/p>\n<p><a id=\"comeback\"><\/a>Now &#8211; we&#8217;ve seen that this works with aqueous acid [H<sub>3<\/sub>O+]. Can we extend this to other nucleophiles? Sure! With some reservations that we&#8217;ll get to in a second.<\/p>\n<h2><a id=\"three\"><\/a>3. What About Other Nucleophiles? Alcohols And HX Also Work<\/h2>\n<p>Changing the solvent from water to an alcohol will result in the alcohol adding instead. For example if we were to use CH<sub>3<\/sub>OH as solvent instead of water, then our product would contain OCH<sub>3<\/sub> joined to the most substituted position.<\/p>\n<p>Hydrohalic acids [HCl, HBr, and HI] can also work well, forming halohydrins.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15174\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-nucleophiles-besides-water-can-be-used-such-as-alcohols-and-also-hydrohalic-acids.gif\" alt=\"nucleophiles besides water can be used such as alcohols and also hydrohalic acids\" width=\"600\" height=\"261\" \/><\/p>\n<h2><a id=\"four\"><\/a>4. When <em>Doesn&#8217;t<\/em> Acid Help? When The Nucleophile Is Not Compatible With Strong Acid<\/h2>\n<p>Now, you might think &#8211; if epoxides are made more reactive by treating with acid, then can&#8217;t we extend this to other nucleophiles too? For example, what about NaOH, or NaNH<sub>2<\/sub>, or even Grignard reagents?<\/p>\n<p>Herein lies the dilemma. Acidic conditions are only compatible with nucleophiles that are protonated\u00a0<strong>reversibly<\/strong>. [<span style=\"color: #993366;\"><em>in other words, nucleophiles whose conjugate acids are strong acids &#8211; think pK<sub>a<\/sub> &lt; 0<\/em> <\/span>]. [<a href=\"#notetwo\">Note 2<\/a>]<\/p>\n<p>Can you see a little problem with adding NaOH to a solution of aqueous acid? What do you think might happen?<\/p>\n<p>Kaboom. Well, that&#8217;s an exaggeration. But the acid will protonate NaOH irreversibly, giving us H<sub>2<\/sub>O [recall that <a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/05\/21\/acid-base-reactions-are-fast\/\" target=\"_blank\" rel=\"noopener noreferrer\">acid-base reactions are fast<\/a>]. Similarly, you can imagine what happens on adding NaNH<sub>2<\/sub> to acid or Grignard reagents to acid: the nucleophile is protonated, giving us the conjugate acid.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15175\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/6-with-acid-strongly-basic-nucleophiles-are-not-compatible-so-no-grignard-reagents-no-naoh-no-nanh2-since-base-will-be-protonated.gif\" alt=\"with acid strongly basic nucleophiles are not compatible so no grignard reagents no naoh no nanh2 since base will be protonated\" width=\"600\" height=\"458\" \/><\/p>\n<h2><a id=\"five\"><\/a>5. What About Opening Under Basic Conditions?<\/h2>\n<p>There&#8217;s still one mystery to solve. From the last post you might recall that if we just add NaOH &#8211; no acid &#8211; to the epoxide we met above, we get a different product altogether.<\/p>\n<p>Note how the stereochemistry at C-2 is completely different\u00a0than with acid.<\/p>\n<p>What might be happening here? Any thoughts? Hint &#8211; it&#8217;s a reaction we&#8217;ve talked about before, and even mentioned in this post.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15176\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/7-opening-of-epoxide-with-naoh-notice-that-attack-happened-at-c2-since-naoh-is-sn2-reaction-with-epoxide.gif\" alt=\"opening of epoxide with naoh notice that attack happened at c2 since naoh is sn2 reaction with epoxide\" width=\"600\" height=\"185\" \/><\/p>\n<p>We&#8217;ll talk about this\u00a0in the next post.<\/p>\n<p><strong>Next Post &#8211; <a href=\"https:\/\/www.masterorganicchemistry.com\/2015\/02\/10\/opening-of-epoxide-with-base\/\">Opening Of Epoxides With Base<\/a><\/strong><\/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\/2015\/02\/10\/opening-of-epoxide-with-base\/\" class=\"\"><span>Epoxide Ring Opening With Base<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2015\/01\/26\/epoxides-the-outlier-of-the-ether-family\/\" class=\"\"><span>Epoxides \u2013 The Outlier Of The Ether Family<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2013\/03\/15\/alkene-bromination-mechanism\/\" class=\"\"><span>Formation of epoxides from bromohydrins (MOC Membership<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2013\/03\/20\/alkene-addition-pattern-2-the-three-membered-ring-pathway\/\" class=\"\"><span>Alkene Addition Pattern #2: The \u201cThree-Membered Ring\u201d Pathway<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/05\/21\/acid-base-reactions-are-fast\/\" class=\"\"><span>Acid Base Reactions Are Fast<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/07\/04\/the-sn2-mechanism\/\" class=\"\"><span>The SN2 Mechanism<\/span><\/a><\/li><\/ul><\/div>\n<p><strong><a id=\"noteone\"><\/a>Note 1:\u00a0<\/strong>Why does the nucleophile attack the more substituted carbon?<\/p>\n<ul>\n<li>In our protonated epoxide, although oxygen bears a positive formal charge, in reality positive charge density mostly resides on carbon [recall that oxygen is more electronegative than carbon].<\/li>\n<li>Recall that positive charge is best stabilized by carbon in the order tertiary &gt; secondary &gt; primary. So in our case, the tertiary carbon atom will bear more positive charge. The tertiary carbon will be more electron-poor (electrophilic)<\/li>\n<li>The length of the C-O bonds will NOT be equal &#8211; the C-O bond to the tertiary carbon is longer and weaker than that of the secondary carbon.<\/li>\n<\/ul>\n<p>Bottom line:<strong> the tertiary carbon is more electrophilic (electron poor) and the C-O bond on the tertiary carbon is weaker, longer, and easier to break.<\/strong><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15177\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/F1-why-does-attack-happen-at-most-substituted-position-of-bromonium-ion-or-mercurinium-ion-or-protonated-epoxide-because-they-have-most-postive-charge.gif\" alt=\"why does attack happen at most substituted position of bromonium ion or mercurinium ion or protonated epoxide because they have most postive charge\" width=\"600\" height=\"258\" \/><\/p>\n<p><strong><a id=\"notetwo\"><\/a>Note 2. <\/strong><a href=\"http:\/\/www.uark.edu\/campus-resources\/mcintosh\/bromonium.html\">These diagrams by Matt McIntosh<\/a> in the same context are very helpful. [<a href=\"#comeback\">back to discussion<\/a>]<\/p>\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\/1401-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<\/p>\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/1402-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<\/p>\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/1405-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<\/p>\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/1407-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<\/p>\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/1406-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\/2415-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<\/p>\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/1409-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<hr \/>\n<h2><a id=\"references\"><\/a>(Advanced) References and Further Reading<\/h2>\n<ol>\n<li><strong>Mechanisms Of Epoxide Reactions<br \/>\n<\/strong> E. Parker and N. S. Isaacs<strong><br \/>\n<\/strong><em>Chemical Reviews<\/em><strong> 1959, <\/strong><em>59<\/em> (4), 737-799<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/cr50028a006\">10.1021\/cr50028a006<\/a><br \/>\nThis review is old but starts with the basics in discussing reactions of epoxides. Both acidic and basic (nucleophilic) reactions are covered.<\/li>\n<li><strong>Synthetic Methods and Reactions; 68<sup>1<\/sup>. Nafion-H-Catalyzed Hydration and Methanolysis of Epoxides<br \/>\n<\/strong>George A. Olah, Alexander P. Fung, David Meidar<strong><br \/>\n<\/strong><em>Synthesis<\/em> <strong>1981<\/strong>; 1981 (<em>4<\/em>): 280-282<br \/>\n<strong>DOI: <\/strong><a href=\"https:\/\/www.thieme-connect.com\/products\/ejournals\/abstract\/10.1055\/s-1981-29414\">1055\/s-1981-29414<\/a><br \/>\nIn this instance, Nafion<sup>TM<\/sup>-H (a polymeric resin developed by DuPont and subsequently modified to the superacidic \u201c-H\u201d form by Prof. Olah) can be used as a catalyst to promote the hydrolytic ring-opening of epoxides to 1,2-diols.<\/li>\n<li><strong>Friedel-Crafts Alkylations of Arenes with Mono- and Bis(trifluoro\u00admethyl)oxiranes in Superacid Medium: Facile Synthesis of \u03b1-(Trifluoro\u00admethyl)- and \u03b1,\u03b1-Bis(Trifluoromethyl)-\u03b2-Arylethanols<br \/>\n<\/strong> K. Surya Prakash, Pablo J. Linares-Palomino, Kevin Glinton, Sujith Chacko, Golam Rasul, Thomas Mathew, and George A. Olah<strong><br \/>\n<\/strong><em>Synlett <\/em><strong>2007<\/strong>, (<em>7<\/em>), 1158-1162<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/www.thieme-connect.com\/products\/ejournals\/abstract\/10.1055\/s-2007-977423\">10.1055\/s-2007-977423<\/a><br \/>\nUnder Br\u00f8nsted acid conditions, epoxides can be used as electrophiles in Friedel-Crafts reactions.<\/li>\n<li><strong>Hot Water-Promoted Ring-Opening of Epoxides and Aziridines by Water and Other Nucleopliles<br \/>\n<\/strong>Zhi Wang, Yong-Tao Cui, Zhao-Bing Xu, and Jin Qu<br \/>\n<em>The Journal of Organic Chemistry<\/em><strong> 2008, <\/strong><em>73<\/em> (6), 2270-2274<br \/>\n<strong>DOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jo702401t\">1021\/jo702401t<\/a><br \/>\nThe title has that typo, which makes me a bit suspicious. On the other hand, this is a <em>JOC<\/em> article, so it <em>should<\/em> be reliable. Turns out that <em>hot water<\/em> can hydrolyze epoxides to diols, no catalyst needed!Epoxides can undergo ring-opening under both acidic and basic conditions \u2013 i.e. under electrophilic and nucleophilic reaction conditions. To take this one step further, in acidic conditions, epoxides can be activated by both Br\u00f8nsted and Lewis acids. Lewis acid catalysis is more common, and is described in the following publications:<\/li>\n<li><strong>Titanium isopropoxide-mediated nucleophilic openings of 2,3-epoxy alcohols. A mild procedure for regioselective ring-opening<br \/>\n<\/strong>Maurice Caron and K. B. Sharpless<br \/>\n<em>The Journal of Organic Chemistry<\/em><strong> 1985, <\/strong><em>50<\/em> (9), 1557-1560<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jo00209a047\">1021\/jo00209a047<\/a><\/li>\n<li><strong>Asymmetric Catalysis of Epoxide Ring-Opening Reactions<br \/>\n<\/strong>Eric N. Jacobsen<strong><br \/>\n<\/strong><em>Accounts of Chemical Research<\/em><strong> 2000, <\/strong><em>33<\/em> (6), 421-431<br \/>\n<strong>DOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ar960061v\">1021\/ar960061v<\/a><br \/>\nProf. Jacobsen (Harvard) has made a career out of developing and studying asymmetric reactions. One of his notable contributions is the development of a Cr(salen) catalyst for the asymmetric ring-opening of epoxides, and the story of the development of this chemistry is described here.<\/li>\n<li><strong>Epoxide opening with tert-butyldimethylsilyl cyanide-zinc iodide. Evidence for a stepwise process in the opening of a sterically hindered epoxide<br \/>\n<\/strong>Paul G. Gassman and Leonard M. Haberman<br \/>\n<em>The Journal of Organic Chemistry<\/em><strong> 1986, <\/strong>51 (25), 5010-5013<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/jo00375a050\">1021\/jo00375a050<\/a><br \/>\nThis is a study of an unusual but interesting reaction developed in the labs of the late Prof P. G. Gassman (U Minnesota). The reaction of epoxides with TMSCN (an organic-soluble and easier-to-handle substitute to traditional cyanide reagents such as KCN) and catalytic ZnI<sub>2<\/sub> gives 1,2-<em>isocyano<\/em> alcohols. This paper is a mechanistic investigation of this reaction.<\/li>\n<li><strong>CONVERSION OF EPOXIDES TO \u03b2-HYDROXY ISOCYANIDES: trans-2-ISOCYANOCYCLOHEXANOL<br \/>\n<\/strong>Paul G. Gassman and Thomas L. Guggenheim<br \/>\n<em>Org. Synth.<\/em><strong> 1986, <\/strong><em>64<\/em>, 39<strong><br \/>\nDOI: <\/strong><a href=\"http:\/\/www.orgsyn.org\/demo.aspx?prep=CV7P0294\">10.15227\/orgsyn.064.0039<\/a><br \/>\nAn <em>Organic Syntheses<\/em> procedure for the ring-opening of epoxides to 1,2-isocyano alcohols.<\/li>\n<\/ol>\n","protected":false},"excerpt":{"rendered":"<p>Opening Epoxides With Aqueous Acid Epoxides can undergo ring-opening with nucleophiles under acidic conditions. In this reaction, the epoxide oxygen is protonated first, making it <\/p>\n","protected":false},"author":1,"featured_media":15169,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_acf_changed":false,"footnotes":""},"categories":[1420],"tags":[1043,1042,903,470,902,887,1041],"post_folder":[],"class_list":["post-8715","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-alcohols-epoxides-ethers","tag-3-membered-ring","tag-aqueous-acid","tag-bromonium","tag-epoxides","tag-halonium","tag-markovnikov","tag-trans-diol"],"acf":[],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.7 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Opening of Epoxides With Acid &#8211; Master Organic Chemistry<\/title>\n<meta name=\"description\" content=\"Epoxides treated with aqueous acid will open to form trans diols. 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