{"id":7067,"date":"2013-02-26T14:11:56","date_gmt":"2013-02-26T19:11:56","guid":{"rendered":"https:\/\/www.masterorganicchemistry.com\/?p=7067"},"modified":"2026-05-07T09:40:59","modified_gmt":"2026-05-07T14:40:59","slug":"rearrangements-in-alkene-addition-reactions","status":"publish","type":"post","link":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/","title":{"rendered":"Rearrangements in Alkene Addition Reactions"},"content":{"rendered":"<p><strong>Carbocation Rearrangements In Alkene Addition Reactions<\/strong><\/p>\n<ul>\n<li>Alkene addition reactions that go through <strong>carbocation intermediates<\/strong> (such as addition of HCl, HBr, HI and H<sub>3<\/sub>O+) may occur with rearrangement of the carbocation intermediate if a more stable carbocation can be formed.<\/li>\n<li>Recall that <strong><a href=\"https:\/\/www.masterorganicchemistry.com\/2011\/03\/11\/3-factors-that-stabilize-carbocations\/\">carbocation stability<\/a><\/strong> increases with substitution, so tertiary carbocations are more stable than secondary carbocations, which are in turn more stable than primary carbocations.<\/li>\n<li>Rearrangements take the form of <strong>hydride shifts<\/strong> where a hydrogen atom and its pair of electrons migrates from an adjacent carbon, resulting in a more stable carbocation, or\u00a0<strong>alkyl shifts<\/strong> where an alkyl group migrates with its pair of electrons.<\/li>\n<li>In certain cases,\u00a0<strong>ring expansion\u00a0<\/strong>reactions may also occur, where formation of a more stable carbocation is accompanied by release of ring strain from a small ring (e.g. cyclobutane)<\/li>\n<\/ul>\n<p><img fetchpriority=\"high\" decoding=\"async\" class=\"alignnone wp-image-37431\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2024\/10\/0-Summary-Alkene-Reactions-With-Rearrangements.gif\" alt=\"Summary-Alkene Reactions With Rearrangements\" width=\"640\" height=\"557\" \/><\/a><\/p>\n<p><strong>Table of Contents<\/strong><\/p>\n<ol>\n<li><a href=\"#one\">An Alkene Addition Reaction With A Twist<\/a><\/li>\n<li><a href=\"#two\">Hydride Shifts In Alkene Additions, Step 1: Attack Of Acid By The Nucleophile<\/a><\/li>\n<li><a href=\"#three\">The Key Rearrangement Step: Hydride Shift<\/a><\/li>\n<li><a href=\"#four\">Step Three: Attack Of Nucleophile On The Carbocation<\/a><\/li>\n<li><a href=\"#five\">Alkene Addition Reactions With Alkyl Shifts<\/a><\/li>\n<li><a href=\"#six\">Alkene Addition Reactions With Ring Expansion<\/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<hr \/>\n<h2><strong><a id=\"one\"><\/a>1. An Addition With A Twist<\/strong><\/h2>\n<p>In exploring reactions that proceed along the <a href=\"https:\/\/www.masterorganicchemistry.com\/2013\/02\/22\/addition-pattern-1-the-carbocation-pathway\/\">carbocation pathway<\/a>, every once in awhile you might see an example of an addition reaction that looks a little\u2026 strange. The alkene is gone, two new bonds have formed, but the positions of the new bonds is a little out of the ordinary. Like in this example!<\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-14991\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/1-hcl-addition-to-alkenes-with-rearrangement-hydride-shift-followed-by-attack-of-cl-.gif\" alt=\"hcl addition to alkenes with rearrangement hydride shift followed by attack of cl-\" width=\"600\" height=\"185\" \/><\/p>\n<p>If you tally up the bonds that form and the bonds that break, we notice that there is an <strong>extra set of C-H bond forming\/breaking events.<\/strong><\/p>\n<p>If you&#8217;ve seen the previous articles in the <a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/08\/15\/rearrangement-reactions-1-hydride-shifts\/\">substitution<\/a> and <a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/11\/09\/elimination-reactions-with-rearrangments\/\">elimination<\/a> series, this should look familiar. It&#8217;s a telltale sign that a rearrangement has taken place.<\/p>\n<h2><strong><a id=\"two\"><\/a>2. Hydride Shifts In Alkene Additions, Step 1: Attack Of Acid By The Nucleophile<\/strong><\/h2>\n<p>The first step in this reaction we&#8217;ve seen before: attack of the alkene upon the electrophile (in this case, the H of H-Cl). The result is a carbocation.<\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-14992\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/2-attack-of-alkene-on-hcl-step-1-of-mechanism-giving-carbocation-secondary.gif\" alt=\"attack of alkene on hcl step 1 of mechanism giving carbocation secondary\" width=\"600\" height=\"207\" \/><\/p>\n<p>Note that the carbocation that&#8217;s been formed is a secondary carbocation, and it&#8217;s adjacent to a tertiary carbon.<\/p>\n<h2><a id=\"three\"><\/a>3. The Key Rearrangement Step: Hydride Shift<\/h2>\n<p>In this next step, the lone pair in the C-H bond migrates from the tertiary carbon to the secondary, forming a new (tertiary) carbocation. The driving force for this reaction is formation of the more stable carbocation.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-14993\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/3-step-2-key-rearrangement-step-from-secondary-carbocation-to-tertiary-carbocation.gif\" alt=\"step 2 key rearrangement step from secondary carbocation to tertiary carbocation\" width=\"600\" height=\"284\" \/><\/p>\n<p>Note how it&#8217;s just one arrow we&#8217;re drawing here! The same arrow shows C-H bond breakage and C-H bond forming.<\/p>\n<h2><a id=\"four\"><\/a>4. Step Three: Attack Of Nucleophile On The Carbocation<\/h2>\n<p>We&#8217;ve also seen the third step before. Attack of the nucleophile (chloride ion) upon the new carbocation gives us our new alkyl halide!<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-14994\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/4-attack-of-halide-nucleophile-on-carbocation-giving-substitution-product-after-reaction-with-nucleophile.gif\" alt=\"attack of halide nucleophile on carbocation giving substitution product after reaction with nucleophile\" width=\"600\" height=\"168\" \/><\/p>\n<h2><a id=\"five\"><\/a>5. Alkene Addition Reactions With Alkyl Shifts<\/h2>\n<p>Rearrangements can also occur with <strong>alkyl<\/strong> shifts, as seen in the example below. Note again that the rearrangement step is represented by just one curved arrow!<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-14995\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-example-of-alkyl-shift-in-addition-of-hcl-to-alkenes-secondary-carbocation-to-tertiary-carbocation.gif\" alt=\"example of alkyl shift in addition of hcl to alkenes secondary carbocation to tertiary carbocation\" width=\"600\" height=\"341\" \/><\/p>\n<h2><a id=\"six\"><\/a>6. Alkene Addition Reactions With Ring Expansion<\/h2>\n<p>Finally, one of the cases that students often find very difficult is in recognizing reactions that occur with rings (ring expansion or ring contraction). Although perhaps difficult to see, in fact it proceeds through exactly the same mechanism as in the cases above. Note again that we&#8217;re depicting the rearrangement reaction with a single curved arrow.<span style=\"color: #993366;\"><em> [Hint &#8211; if you&#8217;re doing this on your own, it might help to <a style=\"color: #993366;\" href=\"https:\/\/www.masterorganicchemistry.com\/2011\/05\/31\/draw-the-ugly-version-first\/\">draw the ugly version first<\/a>].<\/em><\/span><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-14996\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/6-addition-of-hcl-to-alkenes-with-ring-expansion-cyclobutane-to-cyclopentane.gif\" alt=\"addition of hcl to alkenes with ring expansion cyclobutane to cyclopentane\" width=\"600\" height=\"214\" \/><\/p>\n<p>So why is it that the carbon from the ring migrates, and not the CH<sub>3<\/sub> as before? A fair question. Migration of the CH<sub>3<\/sub> would indeed produce a tertiary carbocation. However, migration of the CH<sub>2<\/sub> from the ring not only produces a tertiary carbon but incrases the size of the ring from 4-membered to 5-membered, which relieves considerable ring strain present in the cyclobutane ring (worth about 26 kcal\/mol).<\/p>\n<p>That about does it for the carbocation pathway of alkene addition reactions. In the next post we&#8217;ll go into the second (of three) major pathways for alkene addition mechanisms.<\/p>\n<p><strong>NEXT POST: <a href=\"https:\/\/www.masterorganicchemistry.com\/2013\/03\/06\/bromination-of-alkenes-how-does-it-work\/\">Bromination of Alkenes &#8211; How Does It Work?<\/a>\u00a0<\/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\/2013\/03\/06\/bromination-of-alkenes-how-does-it-work\/\" class=\"\"><span>Bromination of Alkenes<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2011\/03\/11\/3-factors-that-stabilize-carbocations\/\" class=\"\"><span>3 Factors That Stabilize Carbocations<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/08\/15\/rearrangement-reactions-1-hydride-shifts\/\" class=\"\"><span>Rearrangement Reactions (1) \u2013 Hydride Shifts<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2012\/08\/22\/rearrangement-reactions-2-alkyl-shifts\/\" class=\"\"><span>Carbocation Rearrangement Reactions (2) \u2013 Alkyl Shifts<\/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\/04\/02\/epoxidation-hydroxylation-cyclopropanation-alkene-mechanism\/\" class=\"\"><span>Alkene Addition Pattern #3: The \u201cConcerted\u201d Pathway<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/reaction-guide\/pinacol-rearrangement\/\" class=\"\"><span>Pinacol Rearrangement (MOC Membership)<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/reaction-guide\/additions-to-alkenes-accompanied-by-12-hydride-shifts\/\" class=\"\"><span>Additions to alkenes accompanied by 1,2-hydride shifts (MOC Membership)<\/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><\/ul><\/div>\n<hr \/>\n<h2><a id=\"quizzes\"><\/a>Quiz Yourself!<\/h2>\n<p><br \/>\n<img loading=\"lazy\" decoding=\"async\" class=\"wp-image-36214 aligncenter\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/0622-Front-Image-Only.png\" alt=\"\" width=\"600\" height=\"450\" \/><\/a><\/p>\n<p style=\"text-align: center;\"><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a MOC member<\/strong><\/a> to see the clickable quiz with answers on the back.<\/p>\n<p><br \/>\n<br \/>\n<img loading=\"lazy\" decoding=\"async\" class=\"wp-image-36214 aligncenter\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/0636-Front-Image-Only.png\" alt=\"\" width=\"600\" height=\"450\" \/><\/a><\/p>\n<p style=\"text-align: center;\"><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a MOC member<\/strong><\/a> to see the clickable quiz with answers on the back.<\/p>\n<p><br \/>\n<br \/>\n<img loading=\"lazy\" decoding=\"async\" class=\"wp-image-36214 aligncenter\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/2593-Front-Image-Only.png\" alt=\"\" width=\"600\" height=\"450\" \/><\/a><\/p>\n<p style=\"text-align: center;\"><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a MOC member<\/strong><\/a> to see the clickable quiz with answers on the back.<\/p>\n<p><br \/>\n<br \/>\n<img loading=\"lazy\" decoding=\"async\" class=\"wp-image-36214 aligncenter\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/2594-Front-Image-Only.png\" alt=\"\" width=\"600\" height=\"450\" \/><\/a><\/p>\n<p style=\"text-align: center;\"><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a MOC member<\/strong><\/a> to see the clickable quiz with answers on the back.<\/p>\n<p><br \/>\n<br \/>\n<img loading=\"lazy\" decoding=\"async\" class=\"wp-image-36214 aligncenter\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/2586-Front-Image-Only.png\" alt=\"\" width=\"600\" height=\"450\" \/><\/a><\/p>\n<p style=\"text-align: center;\"><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a MOC member<\/strong><\/a> to see the clickable quiz with answers on the back.<\/p>\n<p><br \/>\n<br \/>\n<img loading=\"lazy\" decoding=\"async\" class=\"wp-image-36214 aligncenter\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/0624-Front-Image-Only.png\" alt=\"\" width=\"600\" height=\"450\" \/><\/a><\/p>\n<p style=\"text-align: center;\"><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a MOC member<\/strong><\/a> to see the clickable quiz with answers on the back.<\/p>\n<p><\/p>\n<hr \/>\n<h2><a id=\"references\"><\/a>(Advanced) References and Further Reading<\/h2>\n<ol>\n<li><strong>Ueber die Beziehung der Pinenhalo\u00efdhydrate zu den Halo\u00efdanhydriden des Borneols<br \/>\n<\/strong>Georg Wagner, W. Brickner<strong><br \/>\n<\/strong><em> Ber.<\/em> <strong>1899<\/strong>, <em>32<\/em> (2), 2302-2325<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/abs\/10.1002\/cber.189903202168\">10.1002\/cber.189903202168<\/a><br \/>\nThe oldest examples of these rearrangements are in the pinene series. Wagner showed these rearrangements occur in conversions of pinene to bornyl compounds.<\/li>\n<li><strong>\u00dcber die Gleichgewichts\u2010Isomerie zwischen Bornylchlorid, Isobornylchlorid und Camphen\u2010chlorhydrat<\/strong><br \/>\nHans Meerwein and Konrad van Emster<br \/>\n<em> Ber.<\/em> <strong>1922<\/strong>, <em>55<\/em> (8), 2500-2528<br \/>\n<strong>DOI<\/strong>: <a href=\"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/abs\/10.1002\/cber.19220550829\">10.1002\/cber.19220550829<\/a><br \/>\nProf. Hans Meerwein extended Wagner&#8217;s work to non-terpene series, and came up with the crucial insight that it proceeded through a carbonium ion &#8211; a very controversial insight at the time! Crucial experiment was finding rate was dependent on solvent polarity. Rate order was SO<sub>2<\/sub> &gt; MeNO<sub>2<\/sub> &gt; MeCN &gt; PhNO<sub>2<\/sub> &gt; PhCN &gt; PhOMe &gt; PhBr &gt; EtBr &gt; PhCl &gt; C<sub>6<\/sub>H<sub>6<\/sub> &gt; pet ether &gt; ether. Furthermore, he found that certain acids considerably accelerated the rearrangement of camphene hydrochloride to isobornyl chloride. Alkyl migrations in carbocations are often called \u201cWagner-Meerwein\u201d rearrangements after Georg Wagner and Prof. Hans Meerwein, who studied them more rigorously.<\/li>\n<li><strong> Mechanism of substitution at a saturated carbon atom. Part XXXII. The r\u00f4le of steric hindrance. (Section G) magnitude of steric effects, range of occurrence of steric and polar effects, and place of the Wagner Rearrangement in nucleophilic substitution and elimination<br \/>\n<\/strong>I. Dostrovsky, E. D. Hughes, and C. K. Ingold<strong><br \/>\n<\/strong><em>J. Chem. Soc.<\/em> <strong>1946<\/strong>, 173-194<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.rsc.org\/en\/content\/articlelanding\/1946\/jr\/jr9460000173#!divAbstract\">10.1039\/JR9460000173<\/a><br \/>\nProf. Ingold formalized rules for carbocations:<strong><br \/>\n<\/strong>1) It is necessary for rearrangement that initial bond breakage result in an atom with an incomplete octet<strong><br \/>\n<\/strong>2) The system will only rearrange if the free energy change is in the right direction (i.e. the carbocation being rearranged to should be more stable, e.g. secondary -&gt; tertiary).<strong><br \/>\n<\/strong>This tied together S<sub>N<\/sub>1, E1, alkene addition with Wagner-Meerwein shifts in a unified framework.<\/li>\n<li><strong>Communications TO THE EDITOR<br \/>\n<\/strong><em>The Journal of Organic Chemistry<\/em> <strong>1962,<\/strong> <em>27<\/em> (5), 1926-1932<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jo01052a098\">10.1021\/jo01052a098<\/a><strong><br \/>\n<\/strong>Rigid steroid and diterpenoid systems show addition reactions where multiple hydride and alkyl shifts can occur. One example is dihydroipimaric acid.<\/li>\n<li><strong>The constitution and stereochemistry of euphol<br \/>\n<\/strong> H. R. Barton, J. F. McGhie, M. K. Pradhan, and S. A. Knight<strong><br \/>\n<\/strong><em>J. Chem. Soc.<\/em> <strong>1955<\/strong>, 876-886<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.rsc.org\/en\/content\/articlelanding\/1955\/JR\/JR9550000876#!divAbstract\">10.1039\/JR9550000876<\/a><br \/>\nEuphenol, which is similar to lanosterol, also undergoes addition via a carbocation intermediate which can undergo successive hydride and alkyl shifts.<\/li>\n<li><strong>The Structures of the Triterpenes Friedelin and Cerin<br \/>\n<\/strong>E. J. Corey and J. J. Ursprung<strong><br \/>\n<\/strong><em>Journal of the American Chemical Society<\/em> <strong>1956,<\/strong> <em>78<\/em> (19), 5041-5051<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja01600a064\">10.1021\/ja01600a064<\/a><br \/>\nThe path from Friedelin to Cerin is a crazy series of fun rearrangements!<\/li>\n<li><strong>Total synthesis of (\u00b1)-isocomene and related studies<br \/>\n<\/strong>Michael C. Pirrung<strong><br \/>\n<\/strong><em>Journal of the American Chemical Society<\/em> <strong>1981,<\/strong> <em>103<\/em> (1), 82-87<br \/>\n<strong>DOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja00391a016\">1021\/ja00391a016<\/a><br \/>\nThe rearrangement of vinyl cyclobutane opening to cyclopentane is accompanied by relief of ring strain, and this paper shows that can be applied fruitfully in sesquiterpene synthesis.<\/li>\n<li><strong>The Addition of Hydrogen Bromide to Simple Alkenes<br \/>\n<\/strong>Hilton M. Weiss<strong><br \/>\n<\/strong><em>Journal of Chemical Education<\/em><strong> 1995<\/strong>, <em>72<\/em> (9), 848<strong><br \/>\nDOI: <\/strong><a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ed072p848\">1021\/ed072p848<\/a><br \/>\nA simple experiment suitable for undergraduate organic chemistry laboratory courses that demonstrates that it is possible for the intermediate carbocation to rearrange and give different products.<\/li>\n<\/ol>\n","protected":false},"excerpt":{"rendered":"<p>Carbocation Rearrangements In Alkene Addition Reactions Alkene addition reactions that go through carbocation intermediates (such as addition of HCl, HBr, HI and H3O+) may occur <\/p>\n","protected":false},"author":1,"featured_media":37431,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_acf_changed":false,"footnotes":""},"categories":[1418],"tags":[294,864,397,861,293,468],"post_folder":[],"class_list":["post-7067","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-alkene-reactions","tag-addition","tag-alkyl-shift","tag-carbocations","tag-hydride-shift","tag-rearrangements","tag-wagner-meerwein"],"acf":[],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.7 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Rearrangements in Alkene Addition Reactions &#8211; Master Organic Chemistry<\/title>\n<meta name=\"description\" content=\"Alkene addition reactions that go through carbocations sometimes pass through rearrangements. Here we show examples of hydride and alkyl shift mechanisms.\" \/>\n<meta name=\"robots\" content=\"index, follow, max-snippet:-1, max-image-preview:large, max-video-preview:-1\" \/>\n<link rel=\"canonical\" href=\"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/\" \/>\n<meta property=\"og:locale\" content=\"en_US\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Rearrangements in Alkene Addition Reactions &#8211; Master Organic Chemistry\" \/>\n<meta property=\"og:description\" content=\"Alkene addition reactions that go through carbocations sometimes pass through rearrangements. Here we show examples of hydride and alkyl shift mechanisms.\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/\" \/>\n<meta property=\"og:site_name\" content=\"Master Organic Chemistry\" \/>\n<meta property=\"article:publisher\" content=\"https:\/\/www.facebook.com\/Master-Organic-Chemistry-242610599108055\/\" \/>\n<meta property=\"article:published_time\" content=\"2013-02-26T19:11:56+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2026-05-07T14:40:59+00:00\" \/>\n<meta property=\"og:image\" content=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2024\/10\/0-Summary-Alkene-Reactions-With-Rearrangements.gif\" \/>\n\t<meta property=\"og:image:width\" content=\"890\" \/>\n\t<meta property=\"og:image:height\" content=\"774\" \/>\n\t<meta property=\"og:image:type\" content=\"image\/gif\" \/>\n<meta name=\"author\" content=\"James Ashenhurst\" \/>\n<meta name=\"twitter:card\" content=\"summary_large_image\" \/>\n<meta name=\"twitter:label1\" content=\"Written by\" \/>\n\t<meta name=\"twitter:data1\" content=\"James Ashenhurst\" \/>\n\t<meta name=\"twitter:label2\" content=\"Est. reading time\" \/>\n\t<meta name=\"twitter:data2\" content=\"9 minutes\" \/>\n<script type=\"application\/ld+json\" class=\"yoast-schema-graph\">{\"@context\":\"https:\\\/\\\/schema.org\",\"@graph\":[{\"@type\":\"Article\",\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/#article\",\"isPartOf\":{\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/\"},\"author\":{\"name\":\"James Ashenhurst\",\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/#\\\/schema\\\/person\\\/78d83ec7d02b4b7365bade2cedaef80c\"},\"headline\":\"Rearrangements in Alkene Addition Reactions\",\"datePublished\":\"2013-02-26T19:11:56+00:00\",\"dateModified\":\"2026-05-07T14:40:59+00:00\",\"mainEntityOfPage\":{\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/\"},\"wordCount\":1360,\"commentCount\":29,\"publisher\":{\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/#organization\"},\"image\":{\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/#primaryimage\"},\"thumbnailUrl\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/wp-content\\\/uploads\\\/2024\\\/10\\\/0-Summary-Alkene-Reactions-With-Rearrangements.gif\",\"keywords\":[\"addition\",\"alkyl shift\",\"carbocations\",\"hydride shift\",\"rearrangements\",\"wagner meerwein\"],\"articleSection\":[\"Alkene Reactions\"],\"inLanguage\":\"en-US\",\"potentialAction\":[{\"@type\":\"CommentAction\",\"name\":\"Comment\",\"target\":[\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/#respond\"]}]},{\"@type\":\"WebPage\",\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/\",\"url\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/\",\"name\":\"Rearrangements in Alkene Addition Reactions &#8211; Master Organic Chemistry\",\"isPartOf\":{\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/#website\"},\"primaryImageOfPage\":{\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/#primaryimage\"},\"image\":{\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/#primaryimage\"},\"thumbnailUrl\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/wp-content\\\/uploads\\\/2024\\\/10\\\/0-Summary-Alkene-Reactions-With-Rearrangements.gif\",\"datePublished\":\"2013-02-26T19:11:56+00:00\",\"dateModified\":\"2026-05-07T14:40:59+00:00\",\"description\":\"Alkene addition reactions that go through carbocations sometimes pass through rearrangements. Here we show examples of hydride and alkyl shift mechanisms.\",\"breadcrumb\":{\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/#breadcrumb\"},\"inLanguage\":\"en-US\",\"potentialAction\":[{\"@type\":\"ReadAction\",\"target\":[\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/\"]}]},{\"@type\":\"ImageObject\",\"inLanguage\":\"en-US\",\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/#primaryimage\",\"url\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/wp-content\\\/uploads\\\/2024\\\/10\\\/0-Summary-Alkene-Reactions-With-Rearrangements.gif\",\"contentUrl\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/wp-content\\\/uploads\\\/2024\\\/10\\\/0-Summary-Alkene-Reactions-With-Rearrangements.gif\",\"width\":890,\"height\":774,\"caption\":\"Summary-Alkene Reactions With Rearrangements\"},{\"@type\":\"BreadcrumbList\",\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/2013\\\/02\\\/26\\\/rearrangements-in-alkene-addition-reactions\\\/#breadcrumb\",\"itemListElement\":[{\"@type\":\"ListItem\",\"position\":1,\"name\":\"Home\",\"item\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/\"},{\"@type\":\"ListItem\",\"position\":2,\"name\":\"Rearrangements in Alkene Addition Reactions\"}]},{\"@type\":\"WebSite\",\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/#website\",\"url\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/\",\"name\":\"Master Organic Chemistry\",\"description\":\"\",\"publisher\":{\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/#organization\"},\"potentialAction\":[{\"@type\":\"SearchAction\",\"target\":{\"@type\":\"EntryPoint\",\"urlTemplate\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/?s={search_term_string}\"},\"query-input\":{\"@type\":\"PropertyValueSpecification\",\"valueRequired\":true,\"valueName\":\"search_term_string\"}}],\"inLanguage\":\"en-US\"},{\"@type\":\"Organization\",\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/#organization\",\"name\":\"Master Organic Chemistry\",\"url\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/\",\"logo\":{\"@type\":\"ImageObject\",\"inLanguage\":\"en-US\",\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/#\\\/schema\\\/logo\\\/image\\\/\",\"url\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/wp-content\\\/uploads\\\/2019\\\/04\\\/cutmypic.png\",\"contentUrl\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/wp-content\\\/uploads\\\/2019\\\/04\\\/cutmypic.png\",\"width\":225,\"height\":225,\"caption\":\"Master Organic Chemistry\"},\"image\":{\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/#\\\/schema\\\/logo\\\/image\\\/\"},\"sameAs\":[\"https:\\\/\\\/www.facebook.com\\\/Master-Organic-Chemistry-242610599108055\\\/\"]},{\"@type\":\"Person\",\"@id\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/#\\\/schema\\\/person\\\/78d83ec7d02b4b7365bade2cedaef80c\",\"name\":\"James Ashenhurst\",\"image\":{\"@type\":\"ImageObject\",\"inLanguage\":\"en-US\",\"@id\":\"https:\\\/\\\/secure.gravatar.com\\\/avatar\\\/f9e9df435875e5e6b0bdff6b8522a7279d5717644b3efa7299da22c837bf9fcf?s=96&d=retro&r=g\",\"url\":\"https:\\\/\\\/secure.gravatar.com\\\/avatar\\\/f9e9df435875e5e6b0bdff6b8522a7279d5717644b3efa7299da22c837bf9fcf?s=96&d=retro&r=g\",\"contentUrl\":\"https:\\\/\\\/secure.gravatar.com\\\/avatar\\\/f9e9df435875e5e6b0bdff6b8522a7279d5717644b3efa7299da22c837bf9fcf?s=96&d=retro&r=g\",\"caption\":\"James Ashenhurst\"},\"description\":\"Ph.D. 2006, McGill University (James L. Gleason). Postdoctoral Associate, 2008-2010, Massachusetts Institute of Technology (M. Movassaghi). Founder, Master Organic Chemistry, 2010-present.\",\"sameAs\":[\"https:\\\/\\\/www.masterorganicchemistry.com\\\/about\\\/\"],\"url\":\"https:\\\/\\\/www.masterorganicchemistry.com\\\/author\\\/james\\\/\"}]}<\/script>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"Rearrangements in Alkene Addition Reactions &#8211; Master Organic Chemistry","description":"Alkene addition reactions that go through carbocations sometimes pass through rearrangements. Here we show examples of hydride and alkyl shift mechanisms.","robots":{"index":"index","follow":"follow","max-snippet":"max-snippet:-1","max-image-preview":"max-image-preview:large","max-video-preview":"max-video-preview:-1"},"canonical":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/","og_locale":"en_US","og_type":"article","og_title":"Rearrangements in Alkene Addition Reactions &#8211; Master Organic Chemistry","og_description":"Alkene addition reactions that go through carbocations sometimes pass through rearrangements. Here we show examples of hydride and alkyl shift mechanisms.","og_url":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/","og_site_name":"Master Organic Chemistry","article_publisher":"https:\/\/www.facebook.com\/Master-Organic-Chemistry-242610599108055\/","article_published_time":"2013-02-26T19:11:56+00:00","article_modified_time":"2026-05-07T14:40:59+00:00","og_image":[{"width":890,"height":774,"url":"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2024\/10\/0-Summary-Alkene-Reactions-With-Rearrangements.gif","type":"image\/gif"}],"author":"James Ashenhurst","twitter_card":"summary_large_image","twitter_misc":{"Written by":"James Ashenhurst","Est. reading time":"9 minutes"},"schema":{"@context":"https:\/\/schema.org","@graph":[{"@type":"Article","@id":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/#article","isPartOf":{"@id":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/"},"author":{"name":"James Ashenhurst","@id":"https:\/\/www.masterorganicchemistry.com\/#\/schema\/person\/78d83ec7d02b4b7365bade2cedaef80c"},"headline":"Rearrangements in Alkene Addition Reactions","datePublished":"2013-02-26T19:11:56+00:00","dateModified":"2026-05-07T14:40:59+00:00","mainEntityOfPage":{"@id":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/"},"wordCount":1360,"commentCount":29,"publisher":{"@id":"https:\/\/www.masterorganicchemistry.com\/#organization"},"image":{"@id":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/#primaryimage"},"thumbnailUrl":"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2024\/10\/0-Summary-Alkene-Reactions-With-Rearrangements.gif","keywords":["addition","alkyl shift","carbocations","hydride shift","rearrangements","wagner meerwein"],"articleSection":["Alkene Reactions"],"inLanguage":"en-US","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/","url":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/","name":"Rearrangements in Alkene Addition Reactions &#8211; Master Organic Chemistry","isPartOf":{"@id":"https:\/\/www.masterorganicchemistry.com\/#website"},"primaryImageOfPage":{"@id":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/#primaryimage"},"image":{"@id":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/#primaryimage"},"thumbnailUrl":"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2024\/10\/0-Summary-Alkene-Reactions-With-Rearrangements.gif","datePublished":"2013-02-26T19:11:56+00:00","dateModified":"2026-05-07T14:40:59+00:00","description":"Alkene addition reactions that go through carbocations sometimes pass through rearrangements. Here we show examples of hydride and alkyl shift mechanisms.","breadcrumb":{"@id":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/#breadcrumb"},"inLanguage":"en-US","potentialAction":[{"@type":"ReadAction","target":["https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/"]}]},{"@type":"ImageObject","inLanguage":"en-US","@id":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/#primaryimage","url":"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2024\/10\/0-Summary-Alkene-Reactions-With-Rearrangements.gif","contentUrl":"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2024\/10\/0-Summary-Alkene-Reactions-With-Rearrangements.gif","width":890,"height":774,"caption":"Summary-Alkene Reactions With Rearrangements"},{"@type":"BreadcrumbList","@id":"https:\/\/www.masterorganicchemistry.com\/2013\/02\/26\/rearrangements-in-alkene-addition-reactions\/#breadcrumb","itemListElement":[{"@type":"ListItem","position":1,"name":"Home","item":"https:\/\/www.masterorganicchemistry.com\/"},{"@type":"ListItem","position":2,"name":"Rearrangements in Alkene Addition Reactions"}]},{"@type":"WebSite","@id":"https:\/\/www.masterorganicchemistry.com\/#website","url":"https:\/\/www.masterorganicchemistry.com\/","name":"Master Organic Chemistry","description":"","publisher":{"@id":"https:\/\/www.masterorganicchemistry.com\/#organization"},"potentialAction":[{"@type":"SearchAction","target":{"@type":"EntryPoint","urlTemplate":"https:\/\/www.masterorganicchemistry.com\/?s={search_term_string}"},"query-input":{"@type":"PropertyValueSpecification","valueRequired":true,"valueName":"search_term_string"}}],"inLanguage":"en-US"},{"@type":"Organization","@id":"https:\/\/www.masterorganicchemistry.com\/#organization","name":"Master Organic Chemistry","url":"https:\/\/www.masterorganicchemistry.com\/","logo":{"@type":"ImageObject","inLanguage":"en-US","@id":"https:\/\/www.masterorganicchemistry.com\/#\/schema\/logo\/image\/","url":"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/04\/cutmypic.png","contentUrl":"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/04\/cutmypic.png","width":225,"height":225,"caption":"Master Organic Chemistry"},"image":{"@id":"https:\/\/www.masterorganicchemistry.com\/#\/schema\/logo\/image\/"},"sameAs":["https:\/\/www.facebook.com\/Master-Organic-Chemistry-242610599108055\/"]},{"@type":"Person","@id":"https:\/\/www.masterorganicchemistry.com\/#\/schema\/person\/78d83ec7d02b4b7365bade2cedaef80c","name":"James Ashenhurst","image":{"@type":"ImageObject","inLanguage":"en-US","@id":"https:\/\/secure.gravatar.com\/avatar\/f9e9df435875e5e6b0bdff6b8522a7279d5717644b3efa7299da22c837bf9fcf?s=96&d=retro&r=g","url":"https:\/\/secure.gravatar.com\/avatar\/f9e9df435875e5e6b0bdff6b8522a7279d5717644b3efa7299da22c837bf9fcf?s=96&d=retro&r=g","contentUrl":"https:\/\/secure.gravatar.com\/avatar\/f9e9df435875e5e6b0bdff6b8522a7279d5717644b3efa7299da22c837bf9fcf?s=96&d=retro&r=g","caption":"James Ashenhurst"},"description":"Ph.D. 2006, McGill University (James L. Gleason). Postdoctoral Associate, 2008-2010, Massachusetts Institute of Technology (M. Movassaghi). Founder, Master Organic Chemistry, 2010-present.","sameAs":["https:\/\/www.masterorganicchemistry.com\/about\/"],"url":"https:\/\/www.masterorganicchemistry.com\/author\/james\/"}]}},"_links":{"self":[{"href":"https:\/\/www.masterorganicchemistry.com\/wp-json\/wp\/v2\/posts\/7067","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.masterorganicchemistry.com\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.masterorganicchemistry.com\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.masterorganicchemistry.com\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.masterorganicchemistry.com\/wp-json\/wp\/v2\/comments?post=7067"}],"version-history":[{"count":0,"href":"https:\/\/www.masterorganicchemistry.com\/wp-json\/wp\/v2\/posts\/7067\/revisions"}],"wp:featuredmedia":[{"embeddable":true,"href":"https:\/\/www.masterorganicchemistry.com\/wp-json\/wp\/v2\/media\/37431"}],"wp:attachment":[{"href":"https:\/\/www.masterorganicchemistry.com\/wp-json\/wp\/v2\/media?parent=7067"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.masterorganicchemistry.com\/wp-json\/wp\/v2\/categories?post=7067"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.masterorganicchemistry.com\/wp-json\/wp\/v2\/tags?post=7067"},{"taxonomy":"post_folder","embeddable":true,"href":"https:\/\/www.masterorganicchemistry.com\/wp-json\/wp\/v2\/post_folder?post=7067"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}