{"id":9090,"date":"2013-01-10T11:09:46","date_gmt":"2013-01-10T11:09:46","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=9090"},"modified":"2013-02-14T08:07:48","modified_gmt":"2013-02-14T08:07:48","slug":"a-conflation-of-concepts-conformation-and-pericyclic","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9090","title":{"rendered":"A conflation of concepts: Conformation and pericyclic."},"content":{"rendered":"<div class=\"kcite-section\" kcite-section-id=\"9090\">\n<p>This is an interesting result I got when studying the [1,4] sigmatropic rearrangement of\u00a0heptamethylbicyclo-[3.1.0]hexenyl cations. It fits into the last lecture of a series on pericyclic mechanisms, and just before the first lecture on conformational analysis. This is how they join.<\/p>\n<p><img decoding=\"async\" class=\"aligncenter size-full wp-image-9091\" alt=\"14me\" src=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/01\/14me.svg\" \/><\/p>\n<p>The experiment it relates to<span id=\"cite_ITEM-9090-0\" name=\"citation\"><a href=\"#ITEM-9090-0\">[1]<\/a><\/span> may well be a contender for the top ten list of most influential experiments ever conducted in chemistry. At -40\u00b0C, the <sup>1<\/sup>H NMR spectrum of this species has three peaks, at\u00a0\u03b42.06, 1.57 and 1.13 ppm with an integral ratio of 15:3:3. The five basal methyls are averaged to 2.06 ppm, whereas those marked above as <span style=\"color: #ff0000;\"><strong>Me<sub>a<\/sub><\/strong><\/span> and <span style=\"color: #3366ff;\"><strong>Me<sub>b<\/sub><\/strong> <\/span>exhibit distinct separate resonances. At\u00a0-90\u00b0C, the five basal methyls split into peaks at \u03b42.48, 2.02, 1.66, in the integral ratio of 6:3:6. This indicates a process that is slow at the lower temperature but becomes fast (on the NMR time scale) at the higher temperature. The process must retain the individual identity of\u00a0Me<sub>a<\/sub>\u00a0and Me<sub>b<\/sub>.<\/p>\n<p>The explanation is of course that a pericyclic [1,4] sigmatropic shift occurs. As a four electron process, this must have one antarafacial component, and this is by far easier to achieve by inverting the configuration at the migrating carbon centre. To convince oneself that this process does indeed retain the individual identity of\u00a0Me<sub>a<\/sub>\u00a0and Me<sub>b<\/sub>, an <a href=\"http:\/\/hdl.handle.net\/10042\/22412\" target=\"_blank\">IRC of the reaction<\/a> can be computed (\u03c9B97XD\/6-311G).<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter  class=\" alt=\"Click for  3D.\" src=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/01\/14me.gif\" width=\"391\" height=\"381\" \/><\/p>\n<p>The energy profile is smooth and springs no surprises. The barrier is about right for the temperatures noted above. <img decoding=\"async\" class=\"aligncenter size-full wp-image-9096\" alt=\"14meE\" src=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/01\/14meE.svg\" width=\"400\" \/><\/p>\n<p>But the RMS gradient norm along the IRC is unexpected.\u00a0<img decoding=\"async\" class=\"aligncenter size-full wp-image-9095\" alt=\"14meG\" src=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/01\/14meG.svg\" width=\"400\" \/><\/p>\n<ol>\n<li>Between the limits IRC\u00a0\u00b1 9, the profile is that of a reaction, involving bonds breaking and forming.<\/li>\n<li>In the range IRC\u00a0\u00b1 (9 &#8211; 15), unexpected features appear (hidden intermediates if you check <a href=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=9018\" target=\"_blank\">this post<\/a>). A whole plethora of them. This is the conformational region where the <a href=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=5087\" target=\"_blank\">methyl flags<\/a> start waving (and no bonds are formed or broken). If you watch the animation above very carefully, you will note that the methyl groups start rotating at the start and at the end of the migration, at a stage when the ring has an allyl cation. This delocalised cation has a different impact upon the conformation of the methyl groups from that of the transition state, where the charge now resides largely on the migrating carbon, and the ring now has just a neutral butadiene. This latter imparts a different conformational preference upon the methyl groups. You can see an orbital analysis of these effects at <a href=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=5040\" target=\"_blank\">this post<\/a>.<\/li>\n<li>But perhaps the most surprising aspect of all of this is that each methyl flag waves at a different time from the others; first one waves, then the second and then the third. The two remaining basal methyls (attached to sp<sup>3<\/sup> carbons) do not wave at all.<\/li>\n<\/ol>\n<p>So this classic reaction is not just a pericyclic exemplar, it also illustrates nicely and concisely the conformational analysis of methyl groups interacting with an unsaturated system. Two for the price of one so to speak.<\/p>\n<h2>References<\/h2>\n    <ol class=\"kcite-bibliography csl-bib-body\"><li id=\"ITEM-9090-0\">R.F. Childs, and S. Winstein, \"Ring opening and fivefold degenerate scrambling in hexa- and heptamethylbicyclo[3.1.0]hexenyl cations\", <i>Journal of the American Chemical Society<\/i>, vol. 90, pp. 7146-7147, 1968. <a href=\"https:\/\/doi.org\/10.1021\/ja01027a059\">https:\/\/doi.org\/10.1021\/ja01027a059<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> <!-- kcite-section 9090 -->","protected":false},"excerpt":{"rendered":"<p>This is an interesting result I got when studying the [1,4] sigmatropic rearrangement of\u00a0heptamethylbicyclo-[3.1.0]hexenyl cations. It fits into the last lecture of a series on pericyclic mechanisms, and just before the first lecture on conformational analysis. This is how they join. The experiment it relates to may well be a contender for the top ten [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"activitypub_content_warning":"","activitypub_content_visibility":"","activitypub_max_image_attachments":5,"activitypub_interaction_policy_quote":"anyone","activitypub_status":"","footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2}},"categories":[],"tags":[17,931,2650,843,373],"ppma_author":[2661],"class_list":["post-9090","post","type-post","status-publish","format-standard","hentry","tag-conformational-analysis","tag-energy-profile","tag-pericyclic","tag-reaction-mechanism","tag-tutorial-material"],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.5 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>A conflation of concepts: Conformation and pericyclic. - Henry Rzepa&#039;s Blog<\/title>\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.ch.ic.ac.uk\/rzepa\/blog\/?p=9090\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"A conflation of concepts: Conformation and pericyclic. - Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"og:description\" content=\"This is an interesting result I got when studying the [1,4] sigmatropic rearrangement of\u00a0heptamethylbicyclo-[3.1.0]hexenyl cations. It fits into the last lecture of a series on pericyclic mechanisms, and just before the first lecture on conformational analysis. This is how they join. The experiment it relates to may well be a contender for the top ten [&hellip;]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9090\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"article:published_time\" content=\"2013-01-10T11:09:46+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2013-02-14T08:07:48+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/01\/14me.svg\" \/>\n<meta name=\"author\" content=\"Henry Rzepa\" \/>\n<meta name=\"twitter:card\" content=\"summary_large_image\" \/>\n<meta name=\"twitter:label1\" content=\"Written by\" \/>\n\t<meta name=\"twitter:data1\" content=\"Henry Rzepa\" \/>\n\t<meta name=\"twitter:label2\" content=\"Estimated reading time\" \/>\n\t<meta name=\"twitter:data2\" content=\"2 minutes\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"A conflation of concepts: Conformation and pericyclic. - Henry Rzepa&#039;s Blog","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.ch.ic.ac.uk\/rzepa\/blog\/?p=9090","og_locale":"en_GB","og_type":"article","og_title":"A conflation of concepts: Conformation and pericyclic. - Henry Rzepa&#039;s Blog","og_description":"This is an interesting result I got when studying the [1,4] sigmatropic rearrangement of\u00a0heptamethylbicyclo-[3.1.0]hexenyl cations. It fits into the last lecture of a series on pericyclic mechanisms, and just before the first lecture on conformational analysis. This is how they join. The experiment it relates to may well be a contender for the top ten [&hellip;]","og_url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9090","og_site_name":"Henry Rzepa&#039;s Blog","article_published_time":"2013-01-10T11:09:46+00:00","article_modified_time":"2013-02-14T08:07:48+00:00","og_image":[{"url":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/01\/14me.svg","type":"","width":"","height":""}],"author":"Henry Rzepa","twitter_card":"summary_large_image","twitter_misc":{"Written by":"Henry Rzepa","Estimated reading time":"2 minutes"},"schema":{"@context":"https:\/\/schema.org","@graph":[{"@type":"Article","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9090#article","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9090"},"author":{"name":"Henry Rzepa","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"headline":"A conflation of concepts: Conformation and pericyclic.","datePublished":"2013-01-10T11:09:46+00:00","dateModified":"2013-02-14T08:07:48+00:00","mainEntityOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9090"},"wordCount":499,"commentCount":2,"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9090#primaryimage"},"thumbnailUrl":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/01\/14me.svg","keywords":["conformational analysis","energy profile","pericyclic","Reaction Mechanism","Tutorial material"],"inLanguage":"en-GB","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9090#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9090","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9090","name":"A conflation of concepts: Conformation and pericyclic. - 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The example below is one I have been using as a tutor in organic chemistry for a few years now, and I share\u2026","rel":"","context":"In \"final product\"","block_context":{"text":"final product","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?tag=final-product"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":5763,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5763","url_meta":{"origin":9090,"position":1},"title":"So near and yet so far. The story of the electrocyclic ring opening of a cyclohexadiene.","author":"Henry Rzepa","date":"December 6, 2011","format":false,"excerpt":"My previous three posts set out my take on three principle categories of pericyclic reaction. Here I tell a prequel to the understanding of these reactions. In 1965, Woodward and Hoffmann in their theoretical analysis (submitted Nov 30, 1964) for which the Nobel prize (to Hoffmann only of the pair,\u2026","rel":"","context":"In &quot;Interesting chemistry&quot;","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/12\/ht.gif?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":8375,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=8375","url_meta":{"origin":9090,"position":2},"title":"The regiospecificity of di-imide reduction of an alkene.","author":"Henry Rzepa","date":"November 25, 2012","format":false,"excerpt":"Not a few posts on this blog dissect the mechanisms of well known text-book reactions. But one reaction type where there are few examples on these pages are reductions. These come in three types; using electrons, using a hydride anion and using di-hydrogen. Here I first take a closer look\u2026","rel":"","context":"In \"free energy discrimination\"","block_context":{"text":"free energy discrimination","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?tag=free-energy-discrimination"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2012\/11\/diimide.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":8398,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=8398","url_meta":{"origin":9090,"position":3},"title":"Di-imide reduction with a twist: A M\u00f6bius version.","author":"Henry Rzepa","date":"November 26, 2012","format":false,"excerpt":"I was intrigued by one aspect of the calculated transition state for di-imide reduction of an alkene; the calculated NMR shieldings indicated an diatropic ring current at the centre of the ring, but very deshielded shifts for the hydrogen atoms being transferred. This indicated, like most thermal pericyclic reactions, an\u2026","rel":"","context":"In &quot;Interesting chemistry&quot;","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2012\/11\/GaussViewScreenSnapz004.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":9,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9","url_meta":{"origin":9090,"position":4},"title":"A  Disrotatory 4n+2 electron anti-aromatic M\u00f6bius transition state for a thermal electrocyclic reaction.","author":"Henry Rzepa","date":"April 2, 2009","format":false,"excerpt":"Mauksch and Tsogoeva have recently published an article illustrating how a thermal electrocyclic reaction can proceed with distoratory ring closure, whilst simultaneously also exhibiting 4n electron M\u00f6bius-aromatic character. Why is this remarkable? Because the simple Woodward-Hoffmann rules state that a disrotatory thermal electrocyclic reaction should proceed via a H\u00fcckel-aromatic 4n+2\u2026","rel":"","context":"In &quot;pericyclic&quot;","block_context":{"text":"pericyclic","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=559"},"img":{"alt_text":"Electrocylization of [14] annulene","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/04\/p322.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":11642,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=11642","url_meta":{"origin":9090,"position":5},"title":"Avoided (pericyclic) anti-aromaticity: Reactions of t-butyl-hydroxycarbene.","author":"Henry Rzepa","date":"November 13, 2013","format":false,"excerpt":"Not long ago, I described a cyclic carbene in which elevating the carbene lone pair into a \u03c0-system transformed it from a formally 4n-antiaromatic \u03c0-cycle into a 4n+2 aromatic \u03c0-cycle. From an entirely different area of chemistry, another example of this behaviour emerges; Schreiner's trapping and reactions of t-butyl-hydroxycarbene, as\u2026","rel":"","context":"In &quot;pericyclic&quot;","block_context":{"text":"pericyclic","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=559"},"img":{"alt_text":"H-mig","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/11\/H-mig.gif?resize=350%2C200","width":350,"height":200},"classes":[]}],"jetpack_likes_enabled":false,"authors":[{"term_id":2661,"user_id":1,"is_guest":0,"slug":"admin","display_name":"Henry Rzepa","avatar_url":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","0":null,"1":"","2":"","3":"","4":"","5":"","6":"","7":"","8":""}],"_links":{"self":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/9090","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=9090"}],"version-history":[{"count":11,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/9090\/revisions"}],"predecessor-version":[{"id":9548,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/9090\/revisions\/9548"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=9090"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=9090"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=9090"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=9090"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}