{"id":35402,"date":"2023-08-31T16:18:55","date_gmt":"2023-08-31T21:18:55","guid":{"rendered":"https:\/\/www.masterorganicchemistry.com\/?p=35402"},"modified":"2026-04-19T10:57:33","modified_gmt":"2026-04-19T15:57:33","slug":"oxymercuration-demercuration","status":"publish","type":"post","link":"https:\/\/www.masterorganicchemistry.com\/2023\/08\/31\/oxymercuration-demercuration\/","title":{"rendered":"Oxymercuration Demercuration of Alkenes"},"content":{"rendered":"<p><strong>Oxymercuration Demercuration of Alkenes<\/strong><\/p>\n<ul>\n<li>Treatment of alkenes with mercury (II) salts and water leads to the addition of water and mercury across the C-C pi bond. This is called <strong>oxymercuration<\/strong>.<\/li>\n<li>Addition to the alkene occurs such that OH forms a bond to the <strong>most substituted carbon<\/strong>, making it selective for <strong>Markovnikov<\/strong> products.<\/li>\n<li>The reaction proceeds through attack of the nucleophile on a 3-membered intermediate known as an oxymercurinium ion, which resembles the halonium ion intermediate in reactions such as halogenation of alkenes. As in halogenation, addition occurs to give the products of\u00a0<em>anti<\/em> addition.<\/li>\n<li>In the <strong>demercuration<\/strong> step, mercury is removed by treating the product with sodium borohydride (NaBH<sub>4<\/sub>), giving the alcohol.<\/li>\n<li>By using alcohols instead of H<sub>2<\/sub>O, <strong>ethers<\/strong> can be formed, a reaction known as\u00a0<strong>alkoxymercuration<\/strong>.<\/li>\n<li>Oxymercuration-demercuration is a nice complement to hydroboration-oxidation, which is regioselective for anti-Markovnikov alcohols.<\/li>\n<li>Oxymercuration can also be performed on alkynes (<span style=\"color: #800080;\"><em>see article: <a style=\"color: #800080;\" href=\"https:\/\/www.masterorganicchemistry.com\/2013\/05\/14\/hydroboration-and-oxymercuration-of-alkynes\/\">Hydroboration and Oxymercuration of Akynes<\/a><\/em><\/span>)<\/li>\n<\/ul>\n<p><img fetchpriority=\"high\" decoding=\"async\" class=\"alignnone wp-image-35475\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/0-summary-of-oxymercuration-of-alkenes-with-water-and-mercuric-acetate-demercuration-with-sodium-borohydride.gif\" alt=\"summary of oxymercuration of alkenes with water and mercuric acetate demercuration with sodium borohydride\" width=\"640\" height=\"436\" \/><\/a><\/p>\n<p><strong>Table of Contents<\/strong><\/p>\n<ol>\n<li style=\"list-style-type: none;\">\n<ol>\n<li><a href=\"#one\">Oxymercuration-Demercuration of Alkenes<\/a><\/li>\n<li><a href=\"#two\">Oxymercuration is Regioselective for Markovnikov Products<\/a><\/li>\n<li><a href=\"#three\">The Mechanism for Oxymercuration Proceeds Through Attack of a Nucleophile On A Cyclic Mercurinium Ion<\/a><\/li>\n<li><a href=\"#four\">Understanding Markovnikov Selectivity<\/a><\/li>\n<li><a href=\"#five\">The Demercuration Step<\/a><\/li>\n<li><a href=\"#six\">Oxymercuration Provides &#8220;Markovnikov&#8221; Alcohols Without Rearrangement<\/a><\/li>\n<li><a href=\"#seven\">Addition of Alcohols to Give Ethers<\/a><\/li>\n<li><a href=\"#eight\">Intramolecular Examples<\/a><\/li>\n<li><a href=\"#nine\">Summary<\/a><\/li>\n<li><a href=\"#notes\">Notes<\/a><\/li>\n<li><a href=\"#quizzes\">Quiz Yourself!<\/a><\/li>\n<li><a href=\"#references\">(Advanced) References and Further Reading<\/a><\/li>\n<\/ol>\n<\/li>\n<\/ol>\n<hr \/>\n<h2><a id=\"one\"><\/a>1. Oxymercuration Demercuration of Alkenes<\/h2>\n<p>When an alkene is treated with a mercury(II) salt such as mercuric acetate [Hg(OAc)<sub>2<\/sub>] or mercuric trifluoroacetate Hg(OCOCF<sub>3<\/sub>)<sub>2<\/sub> in the presence of H<sub>2<\/sub>O, <strong>addition<\/strong> occurs across the C-C pi bond, resulting in a new C-OH bond and a C-Hg bond. This reaction is called <strong>oxymercuration<\/strong>.<\/p>\n<p><span style=\"color: #800080;\"><em>It is alternatively called &#8220;solvomercuration&#8221; since addition will generally incorporate any nucleophilic solvent that happens to be around, whether that be H<sub>2<\/sub>O, alcohols, carboxylic acids, or others.\u00a0<\/em><\/span><\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-35421\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/1-general-scheme-for-oxymercuration-demercuration-of-alkenes-with-water-and-nabh4-to-give-markovnikov-alcohols.gif\" alt=\"general scheme for oxymercuration demercuration of alkenes with water and nabh4 to give markovnikov alcohols\" width=\"640\" height=\"485\" \/><\/a><\/p>\n<p>Organomercury compounds tend to be highly <strong>toxic<\/strong> and it is best to avoid handling them if at all possible. [<a href=\"#noteone\"><span style=\"color: #ff0000;\">Note 1<\/span><\/a>] In the <strong>demercuration <\/strong>step, treatment with sodium borohydride (NaBH<sub>4<\/sub>) replaces C-Hg with C-H, resulting in the <strong>alcohol<\/strong> and a little pool of elemental liquid mercury that accumulates at the bottom of the flask.<\/p>\n<h2><a id=\"two\"><\/a>2. Oxymercuration is Regioselective for Markovnikov Products<\/h2>\n<p>Any time two different atoms are added across a C-C pi bond there is the potential for the formation of <strong>constitutional isomers<\/strong>. We saw that in the addition of strong acids (such as H-Br) to alkenes, there is high selectivity for formation of the constitutional isomer where the C-halogen bond forms on the\u00a0<strong>more substituted\u00a0<\/strong>carbon of the alkene, a phenomenon known as &#8220;Markovnikov&#8217;s Rule&#8221; (<span style=\"color: #993366;\"><em>See article &#8211; <span style=\"color: #993366;\"><a style=\"color: #993366;\" href=\"https:\/\/www.masterorganicchemistry.com\/2013\/02\/08\/markovnikovs-rule-1\/\">Markovnikov&#8217;s Rul<\/a><\/span>e<\/em><\/span>).\u00a0 When a reaction shows a strong <strong>preference<\/strong> for the formation of one constitutional isomer over another, we say that reaction is\u00a0<strong>regioselective<\/strong>.<\/p>\n<p>Oxymercuration is also <strong>regioselective <\/strong>for the &#8220;Markovnikov&#8221; alcohol products!<\/p>\n<p>The resulting alcohols that form tend to have the new C-OH bond on the <strong>most substituted\u00a0<\/strong>carbon of the alkene. <span style=\"color: #993366;\"><em>(The selectivity seems to be very<span style=\"color: #993366;\">\u00a0good &#8211; <a style=\"color: #993366;\" href=\"#refthree\">one study<\/a> f<\/span>ound only about a 1% yield of the minor anti-Markovnikov alcohol product)\u00a0<\/em><\/span><\/p>\n<p>The reaction can be carried out on a variety of alkenes to give the products of &#8220;Marknovnikov&#8221; hydration after removal of mercury with NaBH<sub>4<\/sub>.<\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-35422\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/2-simple-examples-of-oxymercuration-reaction-products-from-H-C-Brown-1970-markovnikov-selective.gif\" alt=\"simple examples of oxymercuration reaction products from H C Brown 1970 markovnikov selective\" width=\"640\" height=\"489\" \/><\/a><\/p>\n<p>See if you can predict the product of the reaction below:<\/p>\n<div class=\"wq-quiz-wrapper\" data-id=\"35415\"><style type=\"text\/css\" id=\"wq-flip-custom-css\">.wq-quiz-wrapper[data-id=\"35415\"] {\n--wq-question-width: 100%;\n--wq-question-color: #009cff;\n--wq-question-height: auto;\n--wq-font-color: #444;\n}\n\n\t\t\t.wq-quiz-wrapper[data-id=\"35415\"] {\n\t\t\t\t--wq-question-width: 600px;\n\t\t\t}\n\n\t\t\t@media screen and (max-width: 600px) {\n\t\t\t\t.wq-quiz-wrapper[data-id=\"35415\"] .wq_singleQuestionWrapper { width:100% !important; height:auto !important; }\n\t\t\t}\n\t\t<\/style><!-- wp quiz -->\n<div id=\"wp-quiz-35415\" class=\"wq_quizCtr single flip_quiz wq-quiz wq-quiz-35415 wq-quiz-flip wq-layout-single wq-skin-traditional wq-should-show-correct-answer\" data-quiz-id=\"35415\">\n<div class=\"wq-questions wq_questionsCtr\">\n\t<div class=\"wq-question wq_singleQuestionWrapper wq-question-ihqm5\" data-id=\"ihqm5\">\n\n\t\n\t<div class=\"item_top\">\n\t\t<div class=\"title_container\">\n\t\t\t<div class=\"wq_questionTextCtr\">\n\t\t\t\t<h4 class=\"wq-question-title\"><\/h4>\n\t\t\t<\/div>\n\t\t<\/div>\n\t<\/div>\n\n\t<div class=\"card \">\n\t\t<div class=\"front\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2559-Front.gif\" \/>\n\t\t\n\t\t\n\t\n\t\n\t\t\t<span class=\"top-desc\">Click to Flip<\/span>\n\t<\/div>\n\t\t<div class=\"back\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2559-Reverse.gif\" \/>\n\t\t\n\t\t\n\t\n\t<\/div>\n\t<\/div>\n\n\t\n<\/div>\n<\/div>\n<\/div>\n<!-- \/\/ wp quiz-->\n<\/div><!-- End .wq-quiz-wrapper -->\n<p>If you are given the product of a reaction, and you know the pattern of bonds that form and break, you should be able to work backwards from the product to the starting material, like in the example below:<\/p>\n<div class=\"wq-quiz-wrapper\" data-id=\"35416\"><style type=\"text\/css\" id=\"wq-flip-custom-css\">.wq-quiz-wrapper[data-id=\"35416\"] {\n--wq-question-width: 100%;\n--wq-question-color: #009cff;\n--wq-question-height: auto;\n--wq-font-color: #444;\n}\n\n\t\t\t.wq-quiz-wrapper[data-id=\"35416\"] {\n\t\t\t\t--wq-question-width: 600px;\n\t\t\t}\n\n\t\t\t@media screen and (max-width: 600px) {\n\t\t\t\t.wq-quiz-wrapper[data-id=\"35416\"] .wq_singleQuestionWrapper { width:100% !important; height:auto !important; }\n\t\t\t}\n\t\t<\/style><!-- wp quiz -->\n<div id=\"wp-quiz-35416\" class=\"wq_quizCtr single flip_quiz wq-quiz wq-quiz-35416 wq-quiz-flip wq-layout-single wq-skin-traditional wq-should-show-correct-answer\" data-quiz-id=\"35416\">\n<div class=\"wq-questions wq_questionsCtr\">\n\t<div class=\"wq-question wq_singleQuestionWrapper wq-question-92fll\" data-id=\"92fll\">\n\n\t\n\t<div class=\"item_top\">\n\t\t<div class=\"title_container\">\n\t\t\t<div class=\"wq_questionTextCtr\">\n\t\t\t\t<h4 class=\"wq-question-title\"><\/h4>\n\t\t\t<\/div>\n\t\t<\/div>\n\t<\/div>\n\n\t<div class=\"card \">\n\t\t<div class=\"front\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2560-Front.gif\" \/>\n\t\t\n\t\t\n\t\n\t\n\t\t\t<span class=\"top-desc\">Click to Flip<\/span>\n\t<\/div>\n\t\t<div class=\"back\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2560-Reverse.gif\" \/>\n\t\t\n\t\t\n\t\n\t<\/div>\n\t<\/div>\n\n\t\n<\/div>\n<\/div>\n<\/div>\n<!-- \/\/ wp quiz-->\n<\/div><!-- End .wq-quiz-wrapper -->\n<h2><a id=\"three\"><\/a>3. The Mechanism of Oxymercuration Goes Through A 3-Membered &#8220;Mercurinium Ion&#8221;<\/h2>\n<p>The first step of oxymercuration results in a new <strong>organomercury<\/strong> compound with a C-Hg bond. Unlike many compounds with carbon-metal bonds,\u00a0 organomercury compounds are actually quite stable to handling. [<a href=\"#notetwo\"><span style=\"color: #ff0000;\">Note 2<\/span><\/a>] <span style=\"color: #993366;\"><em>They are (reasonably) stable to air, can be purified with column chromatography, and can even be distilled (!)\u00a0 \u00a0<\/em><\/span><\/p>\n<p>Oxymercuration is stereoselective for <em>anti<\/em>&#8211; addition products.\u00a0 When cyclohexene is treated with Hg(OAc)<sub>2<\/sub> and water, for example, the new -OH and -Hg bonds always form on the <strong>opposite face<\/strong> of the alkene. None of the\u00a0<em>syn<\/em>&#8211; addition product is formed.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-35423\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/5-oxymercuration-demercuration-of-alkenes-proceeds-with-high-stereoselectivity-for-the-anti-products.gif\" alt=\"-oxymercuration demercuration of alkenes proceeds with high stereoselectivity for the anti products\" width=\"640\" height=\"331\" \/><\/a><\/p>\n<p>This high selectivity would rule out an intermediate carbocation, which would be expected to result in a mixture of\u00a0<em>syn<\/em>&#8211; and\u00a0<em>anti-<\/em> addition products. [<span style=\"color: #800080;\"><em>See article &#8211; <a style=\"color: #800080;\" href=\"https:\/\/www.masterorganicchemistry.com\/2013\/02\/22\/addition-pattern-1-the-carbocation-pathway\/\">Alkene Addition Pattern #1 &#8211; The Carbocation Pathway<\/a><\/em>].<\/span><\/p>\n<p>Furthermore, oxymercuration reactions do not give products arising from carbocation rearrangements. [<span style=\"color: #ff0000;\"><em>See section <a href=\"#six\">6<\/a>, below<\/em><\/span>]<\/p>\n<p>The best proposal we have for explaining the stereoselectivity of oxymercuration is that it goes through an intermediate 3-membered &#8220;mercurinium&#8221; ion. (<span style=\"color: #800080;\"><em>Note &#8211; it likely isn&#8217;t crucial for you to remember the name &#8220;mercurinium&#8221; but we still need to call it something<\/em><\/span>).<\/p>\n<p>In the first step, the alkene reacts with Hg<sup>2+<\/sup>\u00a0 to give a three membered ring with a positive formal charge on mercury:<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-35424\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/6-mechanism-for-formation-of-the-mercurinium-ion-in-oxymercuration.gif\" alt=\"-oxymercuration demercuration of alkenes proceeds with high stereoselectivity for the anti products\" width=\"640\" height=\"447\" \/><\/a><\/p>\n<p><span style=\"color: #800080;\"><em>If you have previously covered halogenation of alkenes, this pattern might strike you as familiar, since the mercurinium ion resembles the chloronium, bromonium, and iodonium ion intermediates in the halogenation of alkenes! [See article &#8211; <a style=\"color: #800080;\" href=\"https:\/\/www.masterorganicchemistry.com\/2013\/03\/15\/alkene-bromination-mechanism\/\">Halogenation of Alkenes<\/a>] It is also similar to the structure of protonated epoxides. (This article might also be helpful: <a style=\"color: #800080;\" href=\"https:\/\/www.masterorganicchemistry.com\/2013\/03\/20\/alkene-addition-pattern-2-the-three-membered-ring-pathway\/\">Alkene Addition Pattern #2 &#8211; The &#8220;3-Membered Ring&#8221; Pathway<\/a>] )<\/em><\/span><\/p>\n<p>In acyclic alkenes, this 3-membered bridging ring prevents bond rotation and is responsible for the high stereoselectivity of the reaction.<\/p>\n<p>In the next step, the nucleophile (H<sub>2<\/sub>O) attacks the C-Hg bond from the back, resulting in formation of C-O and breakage of C-Hg.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-35425\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/7-mechanism-of-oxymercuration-step-2-is-attack-of-nucleophile-on-mercurinium-ion-to-give-anti-addition-product.gif\" alt=\"mechanism of oxymercuration step 2 is attack of nucleophile on mercurinium ion to give anti addition product\" width=\"640\" height=\"588\" \/><\/a><\/p>\n<p><span style=\"color: #800080;\"><em>Why from the back and not the front? Because formation of a bond requires donation of a pair of electrons into an <strong>empty<\/strong> orbital, which happens to be the C-Hg sigma* (antibonding) orbital. The C-Hg sigma (bonding) orbital is already full.\u00a0<\/em><\/span><\/p>\n<p>In the case of cyclohexene, addition of H<sub>2<\/sub>O could happen at either carbon with equal likelihood. This will therefore give a racemic mixture of enantiomers.<\/p>\n<p>The final step here is deprotonation of -OH<sub>2<\/sub>(+) to give -OH and one equivalent of acetic acid.<\/p>\n<h2><a id=\"four\"><\/a>4. Understanding Markovnikov Selectivity<\/h2>\n<p>In the case of non-symmetrical mercurinium ions, we are left having to explain why the nucleophile (H<sub>2<\/sub>O) attacks the more substituted carbon and not the less substituted carbon. Furthermore, we have to explain why addition is occurring preferentially via a backside attack on a tertiary carbon, when those who have already learned the S<sub>N<\/sub>2 reaction have been taught that tertiary carbons are more sterically hindered.<\/p>\n<p>I think it&#8217;s helpful to think of the mercurinium ion as being more like a <strong>carbocation<\/strong> than like a tertiary alkyl halide. [<a href=\"#notethree\"><span style=\"color: #ff0000;\">Note 3<\/span><\/a>] We don&#8217;t really worry about steric hindrance when thinking about the nucleophile approaching a tertiary carbocation. In the case of the mercurinium ion, the neighboring mercury is capable of donating a pair of electrons to one face of the carbocation, resulting in a long and weak C-Hg bond.<\/p>\n<p>Think of it as a &#8220;carbocation with benefits&#8221;. :-)<\/p>\n<p>In this vein, imagine some\u00a0 &#8220;resonance forms&#8221; of the mercurinium ion where there is a carbocation on the more substituted carbon and another one with the carbocation on the less substituted carbon. <span style=\"color: #993366;\"><em>I put &#8220;resonance forms&#8221; in quotes here because we teach that you aren&#8217;t really supposed to break single bonds when interconverting resonance forms, but we&#8217;re making an exception here. [<a href=\"#refseven\">Ref<\/a>]\u00a0<\/em><\/span><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-35426\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/8-rationalizing-the-markovnikov-regioselectivity-of-oxymercuration-reactions-as-being-due-to-carbocation-characteristics.gif\" alt=\"rationalizing the markovnikov regioselectivity of oxymercuration reactions as being due to carbocation characteristics\" width=\"640\" height=\"539\" \/><\/a><\/p>\n<p>The resonance form where the positive charge is on the <strong>most substituted carbon<\/strong> will make a greater contribution to the hybrid. It will also have the weakest C-Hg bond and the greatest positive charge density on carbon &#8211; i.e. the greatest electrophilicity.<\/p>\n<p><span style=\"color: #993366;\"><em>But&#8230; why does it still perform a backside attack at the more substituted carbon? Shouldn&#8217;t this be more sterically hindered? Perhaps this is why the rate of oxymercuration reactions go down as substitution on the alkene is increased. More discussion <a style=\"color: #993366;\" href=\"#refseven\">here<\/a>.\u00a0<\/em><\/span><\/p>\n<p>It&#8217;s worth noting that in certain cases where backside attack would be extremely hindered, <em>syn<\/em> addition is observed. See <a href=\"#refeight\">Ref<\/a>.<\/p>\n<h2><a id=\"five\"><\/a>5. Demercuration<\/h2>\n<p>Once oxymercuration is complete, the intermediate organomercury compound is almost never isolated. Instead, <strong>demercuration<\/strong> is performed with sodium borohydride (NaBH<sub>4<\/sub>), which rapidly breaks the C-Hg bond and forms a new C-H bond.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-35427\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/9-demercuration-step-in-oxymercuration-demercuration.gif\" alt=\"demercuration step in oxymercuration demercuration\" width=\"640\" height=\"429\" \/><\/a><\/p>\n<p>Alternatively, demercuration can be carried out with sodium borodeuterohydride (NaBD<sub>4<\/sub>) which allows formation of the deuterated product. <span style=\"color: #993366;\"><em>(Remember that D is just the heavy isotope of H).\u00a0<\/em><\/span><\/p>\n<p>The mechanism of the demercuration step is often not covered in introductory textbooks, but it goes through a free-radical intermediate. <span class=\"s1\">To see a plausible mechanism, <a href=\"\" class=\"custom-tooltip\" data-image=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/Supp-1-mechanism-of-demercuration-reaction-involves-free-radical-intermediates.gif\" data-link=\"\" data-title=\"\" data-text=\"\"> hover here<\/a> or click this <a href=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/Supp-1-mechanism-of-demercuration-reaction-involves-free-radical-intermediates.gif\">link<\/a>. <\/span><\/p>\n<p>Free radicals have a shallow trigonal pyramidal structure and can undergo rapid inversion of their stereochemistry. Therefore, in most cases, generation of the free radical at carbon results in scrambling of its stereochemistry (<span style=\"color: #800080;\"><em>much like the first step of the S<sub>N<\/sub>1<\/em><\/span>).\u00a0 Thus, while the oxymercuration step is stereoselective, the demercuration step is <strong>not<\/strong>. [<span style=\"color: #ff0000;\"><a style=\"color: #ff0000;\" href=\"#notefive\">Note 5<\/a><\/span>]<\/p>\n<h2><strong><a id=\"six\"><\/a>6. Oxymercuration Provides Markovnikov Alcohols Without Rearrangement<\/strong><\/h2>\n<p>We&#8217;ve already learned that one way to get the Markovnikov addition of water across alkenes is just to add aqueous acid.<\/p>\n<p>So why bother having another method?<\/p>\n<p>Well, acid-catalyzed hydration has a serious drawback in that the carbocation intermediate can sometimes undergo rearrangements such as hydride and alkyl shifts. [<span style=\"color: #800080;\"><em>See article &#8211; <a style=\"color: #800080;\" href=\"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/\">Rearrangements in Alkene Addition Reactions<\/a><\/em><\/span>]<\/p>\n<p>See if you can draw the mechanism of this rearrangement, for example.<\/p>\n<div class=\"wq-quiz-wrapper\" data-id=\"35417\"><style type=\"text\/css\" id=\"wq-flip-custom-css\">.wq-quiz-wrapper[data-id=\"35417\"] {\n--wq-question-width: 100%;\n--wq-question-color: #009cff;\n--wq-question-height: auto;\n--wq-font-color: #444;\n}\n\n\t\t\t.wq-quiz-wrapper[data-id=\"35417\"] {\n\t\t\t\t--wq-question-width: 600px;\n\t\t\t}\n\n\t\t\t@media screen and (max-width: 600px) {\n\t\t\t\t.wq-quiz-wrapper[data-id=\"35417\"] .wq_singleQuestionWrapper { width:100% !important; height:auto !important; }\n\t\t\t}\n\t\t<\/style><!-- wp quiz -->\n<div id=\"wp-quiz-35417\" class=\"wq_quizCtr single flip_quiz wq-quiz wq-quiz-35417 wq-quiz-flip wq-layout-single wq-skin-traditional wq-should-show-correct-answer\" data-quiz-id=\"35417\">\n<div class=\"wq-questions wq_questionsCtr\">\n\t<div class=\"wq-question wq_singleQuestionWrapper wq-question-by4b3\" data-id=\"by4b3\">\n\n\t\n\t<div class=\"item_top\">\n\t\t<div class=\"title_container\">\n\t\t\t<div class=\"wq_questionTextCtr\">\n\t\t\t\t<h4 class=\"wq-question-title\"><\/h4>\n\t\t\t<\/div>\n\t\t<\/div>\n\t<\/div>\n\n\t<div class=\"card \">\n\t\t<div class=\"front\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2561-Front.gif\" \/>\n\t\t\n\t\t\n\t\n\t\n\t\t\t<span class=\"top-desc\">Click to Flip<\/span>\n\t<\/div>\n\t\t<div class=\"back\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2561-Reverse.gif\" \/>\n\t\t\n\t\t\n\t\n\t<\/div>\n\t<\/div>\n\n\t\n<\/div>\n<\/div>\n<\/div>\n<!-- \/\/ wp quiz-->\n<\/div><!-- End .wq-quiz-wrapper -->\n<p>One advantage of oxymercuration-demercuration is that rearrangement products are only rarely observed.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-35428\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/11-oxymercuration-of-alkenes-proceeds-without-any-carbocation-rearrangements.gif\" alt=\"oxymercuration of alkenes proceeds without any carbocation rearrangements\" width=\"640\" height=\"228\" \/><\/a><\/p>\n<h2><a id=\"seven\"><\/a>7. Addition of Alcohols to Give Ethers<\/h2>\n<p>Mercurinium ions will react with many different nucleophilic solvents <span style=\"color: #800080;\"><em>(which is why the reaction is often called, &#8220;solvomercuration&#8221;)\u00a0<\/em><\/span><\/p>\n<p>A useful method for making\u00a0<strong>ethers<\/strong> involves using\u00a0 <strong>alcohols\u00a0<\/strong>as the solvent <span style=\"color: #800080;\"><em>(&#8220;alkoxymercuration&#8221;)<\/em><\/span><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-35429\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/12-alkoxymercuration-reactions-are-essentially-similar-to-oxymercuration-reactions-except-the-nucleophile-is-an-alcohol-alternative-way-of-making-ethers.gif\" alt=\"-alkoxymercuration reactions are essentially similar to oxymercuration reactions except the nucleophile is an alcohol - alternative way of making ethers\" width=\"640\" height=\"404\" \/><\/a><\/p>\n<p>Other than the identity of the nucleophile, the mechanism of the reaction is otherwise the same as that for the reaction with water.<\/p>\n<p>See if you can draw the product of the following reaction:<\/p>\n<div class=\"wq-quiz-wrapper\" data-id=\"35418\"><style type=\"text\/css\" id=\"wq-flip-custom-css\">.wq-quiz-wrapper[data-id=\"35418\"] {\n--wq-question-width: 100%;\n--wq-question-color: #009cff;\n--wq-question-height: auto;\n--wq-font-color: #444;\n}\n\n\t\t\t.wq-quiz-wrapper[data-id=\"35418\"] {\n\t\t\t\t--wq-question-width: 600px;\n\t\t\t}\n\n\t\t\t@media screen and (max-width: 600px) {\n\t\t\t\t.wq-quiz-wrapper[data-id=\"35418\"] .wq_singleQuestionWrapper { width:100% !important; height:auto !important; }\n\t\t\t}\n\t\t<\/style><!-- wp quiz -->\n<div id=\"wp-quiz-35418\" class=\"wq_quizCtr single flip_quiz wq-quiz wq-quiz-35418 wq-quiz-flip wq-layout-single wq-skin-traditional wq-should-show-correct-answer\" data-quiz-id=\"35418\">\n<div class=\"wq-questions wq_questionsCtr\">\n\t<div class=\"wq-question wq_singleQuestionWrapper wq-question-thriu\" data-id=\"thriu\">\n\n\t\n\t<div class=\"item_top\">\n\t\t<div class=\"title_container\">\n\t\t\t<div class=\"wq_questionTextCtr\">\n\t\t\t\t<h4 class=\"wq-question-title\"><\/h4>\n\t\t\t<\/div>\n\t\t<\/div>\n\t<\/div>\n\n\t<div class=\"card \">\n\t\t<div class=\"front\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2562-Front.gif\" \/>\n\t\t\n\t\t\n\t\n\t\n\t\t\t<span class=\"top-desc\">Click to Flip<\/span>\n\t<\/div>\n\t\t<div class=\"back\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2562-Reverse.gif\" \/>\n\t\t\n\t\t\n\t\n\t<\/div>\n\t<\/div>\n\n\t\n<\/div>\n<\/div>\n<\/div>\n<!-- \/\/ wp quiz-->\n<\/div><!-- End .wq-quiz-wrapper -->\n<p>An advantage of oxymercuration over some other methods of ether formation is that it can work well for making ethers of secondary and tertiary alcohols.<\/p>\n<p><span style=\"color: #800080;\"><em> S<sub>N<\/sub>2 reactions between alkoxide nucleophiles (RO(-)) and <strong>secondary<\/strong> alkyl halides can run into problems from competing elimination reactions (E2). See this article on <a style=\"color: #800080;\" href=\"https:\/\/www.masterorganicchemistry.com\/2014\/10\/24\/the-williamson-ether-synthesis\/\">The Williamson Ether Synthesis<\/a>.\u00a0<\/em><\/span><\/p>\n<p>See if you can identify some starting materials for the formation of this ether from an alkene and an alcohol.<\/p>\n<div class=\"wq-quiz-wrapper\" data-id=\"35419\"><style type=\"text\/css\" id=\"wq-flip-custom-css\">.wq-quiz-wrapper[data-id=\"35419\"] {\n--wq-question-width: 100%;\n--wq-question-color: #009cff;\n--wq-question-height: auto;\n--wq-font-color: #444;\n}\n\n\t\t\t.wq-quiz-wrapper[data-id=\"35419\"] {\n\t\t\t\t--wq-question-width: 600px;\n\t\t\t}\n\n\t\t\t@media screen and (max-width: 600px) {\n\t\t\t\t.wq-quiz-wrapper[data-id=\"35419\"] .wq_singleQuestionWrapper { width:100% !important; height:auto !important; }\n\t\t\t}\n\t\t<\/style><!-- wp quiz -->\n<div id=\"wp-quiz-35419\" class=\"wq_quizCtr single flip_quiz wq-quiz wq-quiz-35419 wq-quiz-flip wq-layout-single wq-skin-traditional wq-should-show-correct-answer\" data-quiz-id=\"35419\">\n<div class=\"wq-questions wq_questionsCtr\">\n\t<div class=\"wq-question wq_singleQuestionWrapper wq-question-6mikm\" data-id=\"6mikm\">\n\n\t\n\t<div class=\"item_top\">\n\t\t<div class=\"title_container\">\n\t\t\t<div class=\"wq_questionTextCtr\">\n\t\t\t\t<h4 class=\"wq-question-title\"><\/h4>\n\t\t\t<\/div>\n\t\t<\/div>\n\t<\/div>\n\n\t<div class=\"card \">\n\t\t<div class=\"front\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2563-Front.gif\" \/>\n\t\t\n\t\t\n\t\n\t\n\t\t\t<span class=\"top-desc\">Click to Flip<\/span>\n\t<\/div>\n\t\t<div class=\"back\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2563-Reverse.gif\" \/>\n\t\t\n\t\t\n\t\n\t<\/div>\n\t<\/div>\n\n\t\n<\/div>\n<\/div>\n<\/div>\n<!-- \/\/ wp quiz-->\n<\/div><!-- End .wq-quiz-wrapper -->\n<h2><a id=\"eight\"><\/a>8. Intramolecular Examples<\/h2>\n<p>If the molecule has an alkene <strong>and<\/strong> and alcohol, then it can react with itself.<\/p>\n<p>This results in the formation of a cyclic product. Five- and six-membered rings work best.<\/p>\n<p>Instructors love testing their students&#8217; understanding of reactions by surprising them with intramolecular versions of reactions, since they involve no new concepts but are a bit tricky if you haven&#8217;t practiced them.<\/p>\n<p>See if you can draw the product of the reaction below.<\/p>\n<div class=\"wq-quiz-wrapper\" data-id=\"35420\"><style type=\"text\/css\" id=\"wq-flip-custom-css\">.wq-quiz-wrapper[data-id=\"35420\"] {\n--wq-question-width: 100%;\n--wq-question-color: #009cff;\n--wq-question-height: auto;\n--wq-font-color: #444;\n}\n\n\t\t\t.wq-quiz-wrapper[data-id=\"35420\"] {\n\t\t\t\t--wq-question-width: 600px;\n\t\t\t}\n\n\t\t\t@media screen and (max-width: 600px) {\n\t\t\t\t.wq-quiz-wrapper[data-id=\"35420\"] .wq_singleQuestionWrapper { width:100% !important; height:auto !important; }\n\t\t\t}\n\t\t<\/style><!-- wp quiz -->\n<div id=\"wp-quiz-35420\" class=\"wq_quizCtr single flip_quiz wq-quiz wq-quiz-35420 wq-quiz-flip wq-layout-single wq-skin-traditional wq-should-show-correct-answer\" data-quiz-id=\"35420\">\n<div class=\"wq-questions wq_questionsCtr\">\n\t<div class=\"wq-question wq_singleQuestionWrapper wq-question-1z13z\" data-id=\"1z13z\">\n\n\t\n\t<div class=\"item_top\">\n\t\t<div class=\"title_container\">\n\t\t\t<div class=\"wq_questionTextCtr\">\n\t\t\t\t<h4 class=\"wq-question-title\"><\/h4>\n\t\t\t<\/div>\n\t\t<\/div>\n\t<\/div>\n\n\t<div class=\"card \">\n\t\t<div class=\"front\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2564-Front.gif\" \/>\n\t\t\n\t\t\n\t\n\t\n\t\t\t<span class=\"top-desc\">Click to Flip<\/span>\n\t<\/div>\n\t\t<div class=\"back\" >\n\t\n\t\t\t\t\t<img decoding=\"async\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-images\/2564-Reverse.gif\" \/>\n\t\t\n\t\t\n\t\n\t<\/div>\n\t<\/div>\n\n\t\n<\/div>\n<\/div>\n<\/div>\n<!-- \/\/ wp quiz-->\n<\/div><!-- End .wq-quiz-wrapper -->\n<p>When drawing the products of\u00a0<strong>intermolecular\u00a0<\/strong>reactions, it can be very helpful to number the atoms to make sure you don&#8217;t accidentally add (or subtract) any atoms. It can also be helpful to draw an &#8216;ugly version&#8217; of the product first just to get the connectivity right, and then re-draw it nicely.<\/p>\n<h2><a id=\"nine\"><\/a>9. Summary<\/h2>\n<ul>\n<li>One of the key takeaways from this article is to understand the contrast between oxymercuration and acid-catalyzed hydration. Acid-catalyzed hydration will potentially give carbocation rearrangements, but <strong>oxymercuration will not.\u00a0<\/strong><\/li>\n<li>Another is the contrast between the Markovnikov selectivity of oxymercuration and the anti-Markovnikov selectivity of hydroboration.<\/li>\n<li>A third key point is to see the similarity in mechanism between oxymercuration of alkenes, halogenation of alkenes, and the opening of epoxides under acidic conditions.<\/li>\n<\/ul>\n<hr \/>\n<h2><strong><a id=\"notes\"><\/a>Notes<\/strong><\/h2>\n<div class=\"related-articles\"><p><strong>Related Articles<\/strong><\/p><ul><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2013\/05\/14\/hydroboration-and-oxymercuration-of-alkynes\/\" class=\"\"><span>Hydroboration and Oxymercuration of Alkynes<\/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\/2013\/03\/15\/alkene-bromination-mechanism\/\" class=\"\"><span>Halogenation of Alkenes and Halohydrin Formation<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2013\/02\/08\/markovnikovs-rule-1\/\" class=\"\"><span>Markovnikov Addition Of HCl To Alkenes<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2013\/03\/28\/hydroboration-of-alkenes-the-mechanism\/\" class=\"\"><span>Hydroboration Oxidation of Alkenes<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2020\/02\/28\/staggered-vs-eclipsed-conformations-of-ethane\/\" class=\"\"><span>Staggered vs Eclipsed Conformations of Ethane<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2015\/02\/02\/opening-of-epoxides-with-acid\/\" class=\"\"><span>Opening of Epoxides With Acid<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2014\/10\/24\/the-williamson-ether-synthesis\/\" class=\"\"><span>The Williamson Ether Synthesis<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2014\/11\/07\/synthesis-of-ethers-2-back-to-the-future\/\" class=\"\"><span>Ethers From Alkenes, Tertiary Alkyl Halides and Alkoxymercuration<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2023\/09\/15\/hydration-alkenes-acid\/\" class=\"\"><span>Acid-Catalyzed Addition of H2O To Alkenes<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2010\/07\/02\/stereoselective-stereospecific\/\" class=\"\"><span>Stereoselective and Stereospecific Reactions<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2013\/01\/22\/alkene-addition-regioselectivity-syn-anti\/\" class=\"\"><span>Alkene Addition Reactions: \u201cRegioselectivity\u201d and \u201cStereoselectivity\u201d (Syn\/Anti)<\/span><\/a><\/li><\/ul><\/div>\n<p><span style=\"color: #ff0000;\"><strong><span style=\"color: #000000;\"><a id=\"noteone\"><\/a>Note 1.<\/span> Alkylmercury compounds are highly toxic and should not be worked with without proper training and safety equipment<\/strong><\/span>. Dimethylmercury (CH<sub>3<\/sub>)<sub>2<\/sub>Hg is particularly dangerous and has been responsible for numerous fatalities. [<a href=\"https:\/\/pubsapp.acs.org\/cen\/safety\/19970616.html?\">See safety bulletin<\/a>]<\/p>\n<p><strong><a id=\"notetwo\"><\/a>Note 2. <\/strong><a href=\"#refsix\">Chatt<\/a> says:<\/p>\n<blockquote><p>&#8220;Both <em>cis- <\/em>and\u00a0<em>trans<\/em>-1-methoxy-2-chloromercuri)cyclohexanes prepared from cyclohexene can be distilled under reduced pressure without change. <em><strong>Except for their greater density they are typical organic compounds<\/strong><\/em>. &#8220;<\/p><\/blockquote>\n<p><strong><a id=\"notethree\"><\/a>Note 3.\u00a0<\/strong>The structure of the carbon in the mercurinium ion is flatter and more sp<sup>2<\/sup> like than the tetrahedral geometry of the sp<sup>3<\/sup>-hybridized carbon in an alkyl halide, which alleviates steric crowding somewhat.<\/p>\n<p><strong>Note 4.\u00a0<\/strong>Interesting to note the relative reactivity of various alkenes towards oxymercuration. Monosubstituted alkenes are best. Tetrasubstituted alkenes are much slower. With tri- and tetrasubstituted alkenes it is sometimes necessary to use the more electrophilic Hg(OTFA)<sub>2<\/sub>.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-35430\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/F1-relative-reactivity-of-alkenes-in-oxymercuration-reactions-show-that-monosubstituted-alkenes-are-most-reactive.gif\" alt=\"relative reactivity of alkenes in oxymercuration reactions show that monosubstituted alkenes are most reactive\" width=\"640\" height=\"291\" \/><\/a><\/p>\n<p><strong><a id=\"notefive\"><\/a>Note 5.\u00a0<\/strong>A useful scheme from Whitesides&#8217; studies on the mechanism of demercuration that demonstrates a free-radical intermediate was present: demercuration with NaBH4,\u00a0 followed by trapping with oxygen (O<sub>2<\/sub>) led to a mixture of <em>cis<\/em> and <em>trans<\/em> stereoisomers. (<a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja00810a036\"><em>J. Am. Chem. Soc.<\/em>\u00a0<strong>1974,\u00a0<\/strong><em>96<\/em><span style=\"text-decoration: underline;\">,<\/span> 870<\/a>)<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-35477\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/F2-From-Whitesides-JACS-1974-870-.png\" alt=\"From Whitesides JACS 1974 870\" width=\"450\" height=\"579\" srcset=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/F2-From-Whitesides-JACS-1974-870-.png 908w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/F2-From-Whitesides-JACS-1974-870--233x300.png 233w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/F2-From-Whitesides-JACS-1974-870--796x1024.png 796w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/F2-From-Whitesides-JACS-1974-870--768x988.png 768w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2023\/08\/F2-From-Whitesides-JACS-1974-870--591x760.png 591w\" sizes=\"(max-width: 450px) 100vw, 450px\" \/><\/a><\/p>\n<p><strong>Note 6.\u00a0<\/strong>Here is an interactive model of the oxymercurinium ion formed from 2-methylpropene, courtesy of <a href=\"https:\/\/www.rowansci.com\/\">Rowan<\/a>.<\/p>\n<p>Note that this is the oxymercurinium ion of an unsymmetrical alkene. The C-Hg bond to the least substituted carbon is considerably shorter (2.25 \u00c5) than the C-Hg bond to the\u00a0<strong>more\u00a0<\/strong> substituted carbon (2.76 \u00c5 &#8211; such a long bond that it does not even register as a bond in the modeling software).<\/p>\n<p>This goes a long way towards explaining why attack occurs at the more substituted carbon; the C-Hg bond is much longer (and weaker!).<\/p>\n<p><iframe title=\"Oxymercurinium Ion of 2-Methylpropene\" src=\"https:\/\/labs.rowansci.com\/iframe\/calculations\/692bf08d-129a-4732-b474-51a9815d2c84\" width=\"640\" height=\"640\"><\/iframe><\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/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\/3592-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\/3581-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\/0636-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\/3064-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\/3066-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\/3065-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\/2574-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><strong><a id=\"references\"><\/a>(Advanced) References and Further Reading<\/strong><\/h2>\n<ol>\n<li style=\"list-style-type: none;\">\n<ol>\n<li><strong>Ueber das Verhalten von Mercurisalzen gegen Olefine<\/strong><br \/>\nK. A. Hofmann, Julius Sand<br \/>\n<em>Chem. Ber.\u00a0<\/em><strong>1900<\/strong>,\u00a0<em>33<\/em>, 1340-1353.<br \/>\n<strong>DOI: <\/strong><a href=\"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/cber.190003301231\">10.1002\/cber.190003301231<\/a><br \/>\nOne of the earliest reports on the oxymercuration of alkenes, from 1902.<\/li>\n<li><strong>The Co\u00f6rdination Complexes of Mercuric Ion with Cyclohexene<\/strong><br \/>\nH. J. Lucas, F. R. Hepner, and S. Winstein<br \/>\n<em>Journal of the American Chemical Society<\/em> 1939 61 (11), 3102-3106<br \/>\n<strong>DOI<\/strong>:<a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja01266a036\"> 10.1021\/ja01266a036 <\/a><br \/>\nPossibly the first proposal for the mercurinium ion. From the doctoral research of Saul Winstein, who went on to have an exceptionally successful career in physical organic chemistry. Many familiar terms in common usage &#8211; &#8220;neighboring group participation&#8221;, &#8220;nonclassical ions&#8221;, &#8220;anchimeric assistance&#8221;, &#8220;intimate ion pair&#8221;, &#8220;internal return&#8221;, and &#8220;homoaromaticity&#8221; are his coinings. See <a href=\"https:\/\/www.nasonline.org\/publications\/biographical-memoirs\/memoir-pdfs\/winstein-saul.pdf\">here for a biography<\/a>.<\/li>\n<li><strong><a id=\"refthree\"><\/a>Solvomercuration-demercuration. I. Oxymercuration-demercuration of representative olefins in an aqueous system. Mild procedure for the Markovnikov hydration of the carbon-carbon double bond<\/strong><br \/>\nHerbert Charles Brown and Philip J. Geoghegan Jr.<br \/>\n<em>The Journal of Organic Chemistry<\/em> <strong>1970<\/strong> 35 (6), 1844-1850<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/pubs.acs.org\/doi\/epdf\/10.1021\/jo00831a028\">10.1021\/jo00831a028<\/a><br \/>\nThe use of NaBH4 for removing mercury was a relatively late development. This paper from H.C. Brown&#8217;s group is an excellent introduction to oxymercuration with lots of examples on different classes of olefins, relative rate studies, and Markovnikov vs. anti-Markovnikov selectivities. If you were to read just one article on this list, this would be the one to read.<br \/>\n(See also <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja00982a043\"><em>JACS <strong>1967<\/strong> 1522<\/em><\/a> for the initial communication)<\/li>\n<li><strong>Reactions of alkylmercuric halides with sodium borohydride in the presence of molecular oxygen<\/strong><br \/>\nCraig L. Hill and George M. Whitesides<br \/>\n<em>Journal of the American Chemical Society<\/em> <strong>1974<\/strong> 96 (3), 870-876<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja00810a036\">10.1021\/ja00810a036<\/a><br \/>\nStudy of the mechanism of the demercuration step clearly shows that it goes through a free-radical mechanism. The intermediate radical can be trapped with molecular oxygen and gives a mixture of stereoisomers.<\/li>\n<li><strong>Organomercury Compounds in Organic Synthesis\u00a0\u00a0<\/strong><br \/>\nRichard C. Larock<br \/>\n<em>Angewandte Chemie International Edition in English<\/em>,\u00a0<strong>1978<\/strong>,\u00a0<em>27<\/em>, 17<br \/>\n<strong>DOI: <\/strong><a href=\"https:\/\/onlinelibrary.wiley.com\/doi\/abs\/10.1002\/anie.197800271\">10.1002\/anie.197800271<\/a><br \/>\nFairly short and useful review on organomercury compounds in organic chemistry; section 4 deals with oxymercuration.<\/li>\n<li><strong><a id=\"refsix\"><\/a>Addition Compounds of Olefins With Mercuric Salts<br \/>\n<\/strong>J. Chatt<br \/>\n<em>Chemical Reviews<\/em>,\u00a0<strong>1951<\/strong>, <em>48<\/em>, 7<br \/>\n<strong>DOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/cr60149a002\">10.1021\/cr60149a002<\/a><br \/>\nReview of the older literature on oxymercuration up until about 1950, covering different mechanistic proposals.<\/li>\n<li><strong><a id=\"refseven\"><\/a>Studies on the Mechanism of the Oxymercuration of Substituted Cyclohexenes<br \/>\n<\/strong>Daniel J. Pasto and John A. Gontarz<br \/>\n<em>J. Am. Chem. Soc.\u00a0<\/em><strong>1971<\/strong>,\u00a0<em>93<\/em>, 6902.<br \/>\n<strong>DOI: <\/strong><a href=\"https:\/\/doi.org\/10.1021\/ja00754a035\">10.1021\/ja00754a035<\/a><strong><br \/>\n<\/strong>Good discussion here on the regioselectivity of oxymercuration to mercurinium ions with 4-<em>t<\/em>-butyl cyclohexenes. Includes a few examples of &#8220;anti-Markovnikov&#8221; addition products that form for stereoelectronic reasons.<\/li>\n<li><strong><a id=\"refeight\"><\/a>Solvomercuration-demercuration. V. Additions to bicyclic olefins. VI. Stereochemistry of the oxymercuration-demercuration of norbornene, 7,7-dimethylnorbornene, and related olefins<br \/>\n<\/strong>Herbert C. Brown and James H. Kawakami<br \/>\n<em>Journal of the American Chemical Society<\/em> <strong>1973<\/strong> 95 (26), 8665-8669<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja00807a027\">10.1021\/ja00807a027<\/a><br \/>\nOxymercuration on very hindered norbornene system gives\u00a0<em>syn<\/em> products. The authors propose that the mercurinium ion is in equilibrium with a transient cation.<\/li>\n<li><strong>Mechanism of the reduction of organomercurials with sodium borohydride<\/strong><br \/>\nDaniel J. Pasto and John A. Gontarz<br \/>\n<em>Journal of the American Chemical Society<\/em> <strong>1969<\/strong> 91 (3), 719-721<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja01031a036\">10.1021\/ja01031a036<\/a><br \/>\nThe reduction of organomercurials with NaBH<sub>4<\/sub> goes through a free-radical intermediate. In some cases (e.g. cyclopentene) , retention of configuration is high (&gt;95%). In others (e.g. 2-butene) bond rotation is fast relative to recapture.<\/li>\n<\/ol>\n<\/li>\n<\/ol>\n","protected":false},"excerpt":{"rendered":"<p>Oxymercuration Demercuration of Alkenes Treatment of alkenes with mercury (II) salts and water leads to the addition of water and mercury across the C-C pi <\/p>\n","protected":false},"author":1,"featured_media":35475,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_acf_changed":false,"footnotes":""},"categories":[1418],"tags":[294,14858,14855,14857,898,887,14854,14856,358,356],"post_folder":[],"class_list":["post-35402","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-alkene-reactions","tag-addition","tag-alkoxymercuration","tag-anti-addition","tag-demercuration","tag-hydration","tag-markovnikov","tag-mercurinium","tag-mercury","tag-nabh4","tag-oxymercuration"],"acf":[],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.7 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Oxymercuration Demercuration of Alkenes &#8211; Master Organic Chemistry<\/title>\n<meta name=\"description\" content=\"Oxymercuration Demercuration of alkenes gives alcohols with Markovnikov selectivity. 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