{"id":12895,"date":"2014-09-06T13:56:40","date_gmt":"2014-09-06T12:56:40","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=12895"},"modified":"2014-09-16T05:46:38","modified_gmt":"2014-09-16T04:46:38","slug":"computationally-directed-synthesis-23-dimethyl-2-butene-no","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12895","title":{"rendered":"Computationally directed synthesis: 2,3-dimethyl-2-butene + NO(+)."},"content":{"rendered":"
\n

In the previous posts<\/a>, I explored reactions which can be flipped between two potential (stereochemical) outcomes. This triggered a memory from Alex, who pointed out this article from 1999[1]<\/a><\/span> in which the nitrosonium cation as an electrophile can have two outcomes A<\/strong> or B<\/strong> when interacting with the electron-rich 2,3-dimethyl-2-butene. \"NO\"<\/a> NMR evidence clearly pointed to the \u03c0-complex A<\/strong> as being formed, and not the cyclic nitrosonium species B<\/strong> (X=Al4<\/sub>–<\/sup>). If you are wondering where you have seen an analogy for the latter, it would be the species formed when bromine reacts with an alkene (\u2261 Br+<\/sup>, X=Br–<\/sup> or Br3<\/sub>–<\/sup>). The two structures are shown below[1]<\/a><\/span> \"tetramethyletylene-NO+\"<\/a> Since the topic that sparked this concerned pericyclic reactions, it seemed possible that if it had been formed, species B<\/strong> would immediately undergo a pericyclic electrocyclic reaction to form the rather odd-looking cation C, which might\u00a0then be trapped by eg X(-) to form the nitrone D. So this post is an exploration of what happens when X-NO (X= CF3<\/sub>COO, trifluoracetate) interacts with\u00a02,3-dimethyl-2-butene, as an illustration of what can be achieved nowadays from about 2 days worth of dry-lab computation as a prelude to e.g.<\/em> an experiment in the wet-lab (it would take a little more than two days to achieve the latter I suspect). Hence computationally directed synthesis<\/em>. The model is set up as \u03c9B97XD\/6-311G(d,p)\/SCRF=chloroform. A transition state is located[2]<\/a><\/span> and the resulting IRC (below)\u00a0[3]<\/a><\/span> does not quite have the outcome the above scheme would suggest. \"NOa\"<\/a> \"NOe\"<\/a> \"NOg\"<\/a> Neither A<\/strong> nor B<\/strong> is formed; instead it is the tetrahedral species E<\/strong>, which is ~15 kcal\/mol endothermic. \"NOaa\"<\/a> I should immediately point out that this is not inconsistent with the formation of A<\/strong> as previously characterised[1]<\/a><\/span>. That is because this experiment was conducted with a non-nucleophilic counter-anion (X=Al4<\/sub>–<\/sup>), whereas in the computational simulation above, we\u00a0have a nucleophilic<\/em> anion (X= CF3<\/sub>CO2<\/sub>–<\/sup>). What a difference the inclusion of a counter-ion<\/a> in the calculation can have! The barrier however (~35 kcal\/mol) is a little too high for a facile thermal reaction. In the second of this two-stage reaction, E now ring-opens to form the anticipated D[4]<\/a><\/span> with quite a small barrier of ~6 kcal\/mol, but a highly exothermic outcome. I ask this question about it; can this still be described as a pericyclic process? (there is some analogy to the electrocyclic ring opening of a cyclopropyl tosylate<\/a>). \"NOb\"<\/a>\"NObe\"<\/a> So what are the conclusions? Well, because of the rather high initial barrier, the alkene will need activation (by electron donating substituents, perhaps OMe) for the reaction to become more viable. But if it works, it could be an interesting synthesis of nitrones (I have not yet searched to find out if the reaction is actually known).<\/p>\n

References<\/h2>\n
  1. G.I. Borodkin, I.R. Elanov, A.M. Genaev, M.M. Shakirov, and V.G. Shubin, \"Interaction in olefin\u2013NO+ complexes: structure and dynamics of the NO+\u20132,3-dimethyl-2-butene complex\", Mendeleev Communications<\/i>, vol. 9, pp. 83-84, 1999. https:\/\/doi.org\/10.1070\/mc1999v009n02abeh000995<\/a>\n\n<\/li>\n
  2. H.S. Rzepa, \"C8H12F3NO3\", 2014. https:\/\/doi.org\/10.14469\/ch\/24979<\/a>\n\n<\/li>\n
  3. H.S. Rzepa, \"Gaussian Job Archive for C8H12F3NO3\", 2014. https:\/\/doi.org\/10.6084\/m9.figshare.1162797<\/a>\n\n<\/li>\n
  4. H.S. Rzepa, \"Gaussian Job Archive for C8H12F3NO3\", 2014. https:\/\/doi.org\/10.6084\/m9.figshare.1162676<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

    In the previous posts, I explored reactions which can be flipped between two potential (stereochemical) outcomes. This triggered a memory from Alex, who pointed out this article from 1999 in which the nitrosonium cation as an electrophile can have two outcomes A or B when interacting with the electron-rich 2,3-dimethyl-2-butene. NMR evidence clearly pointed to […]<\/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":[559,1086],"tags":[978,1050,1253,721],"ppma_author":[2661],"class_list":["post-12895","post","type-post","status-publish","format-standard","hentry","category-pericyclic","category-reaction-mechanism-2","tag-cf-3","tag-cf-3-co","tag-coo","tag-simulation"],"yoast_head":"\nComputationally directed synthesis: 2,3-dimethyl-2-butene + NO(+). - Henry Rzepa'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=12895\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Computationally directed synthesis: 2,3-dimethyl-2-butene + NO(+). - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"In the previous posts, I explored reactions which can be flipped between two potential (stereochemical) outcomes. This triggered a memory from Alex, who pointed out this article from 1999 in which the nitrosonium cation as an electrophile can have two outcomes A or B when interacting with the electron-rich 2,3-dimethyl-2-butene. NMR evidence clearly pointed to […]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12895\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa's Blog\" \/>\n<meta property=\"article:published_time\" content=\"2014-09-06T12:56:40+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2014-09-16T04:46:38+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2014\/09\/NO.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":"Computationally directed synthesis: 2,3-dimethyl-2-butene + NO(+). - Henry Rzepa'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=12895","og_locale":"en_GB","og_type":"article","og_title":"Computationally directed synthesis: 2,3-dimethyl-2-butene + NO(+). - Henry Rzepa's Blog","og_description":"In the previous posts, I explored reactions which can be flipped between two potential (stereochemical) outcomes. This triggered a memory from Alex, who pointed out this article from 1999 in which the nitrosonium cation as an electrophile can have two outcomes A or B when interacting with the electron-rich 2,3-dimethyl-2-butene. 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Other journals (e.g.\u00a0Nature Chemistry ran the article as a research highlight (where the purpose\u2026","rel":"","context":"In "Interesting chemistry"","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.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2010\/11\/cbd.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":8216,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=8216","url_meta":{"origin":12895,"position":1},"title":"Secrets revealed for conjugate addition to cyclohexenone using a Cu-alkyl reagent.","author":"Henry Rzepa","date":"November 4, 2012","format":false,"excerpt":"The text books say that cyclohexenone A will react with a Grignard reagent by delivery of an alkyl (anion) to the carbon of the carbonyl (1,2-addition) but if dimethyl lithium cuprate is used, a conjugate 1,4-addition proceeds, to give the product B shown below. The standard explanation is that the\u2026","rel":"","context":"In \"metal\"","block_context":{"text":"metal","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?tag=metal"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2012\/11\/4.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":11995,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=11995","url_meta":{"origin":12895,"position":2},"title":"The wrong trousers: the anti-Markovnikov addition of borane to 2-methylpropene.","author":"Henry Rzepa","date":"March 2, 2014","format":false,"excerpt":"A staple of introductory undergraduate teaching in organic chemistry is Markovnikov's rule, which states: \"the addition of a protic acid HX to an alkene results in the acid hydrogen (H) becoming attached to the carbon with fewer alkyl substituents and the halide (X) group to the carbon with more alkyl\u2026","rel":"","context":"In "reaction mechanism"","block_context":{"text":"reaction mechanism","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1086"},"img":{"alt_text":"Click for 3D","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2014\/03\/borane%2Bbutene.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":10145,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10145","url_meta":{"origin":12895,"position":3},"title":"Feist’s acid. Stereochemistry galore.","author":"Henry Rzepa","date":"April 4, 2013","format":false,"excerpt":"Back in the days (1893) when few compounds were known, new ones could end up being named after the discoverer. Thus Feist is known for the compound bearing his name; the 2,3 carboxylic acid of methylenecyclopropane (1, with Me replaced by CO2H). Compound 1 itself nowadays is used to calibrate\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"methylene-cyclopropane","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/04\/methylene-cyclopropane.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":9894,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9894","url_meta":{"origin":12895,"position":4},"title":"To be cyclobutadiene, or not to be, that is the question? You decide.","author":"Henry Rzepa","date":"March 21, 2013","format":false,"excerpt":"A quartet of articles has recently appeared on the topic of cyclobutadiene.,,,. You will find a great deal discussed there, but I can boil it down to this essence. Do the following coordinates (obtained from a (disordered) previously published x-ray refinement) correspond to a van der Waals complex of 1,3-dimethyl\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":1158,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=1158","url_meta":{"origin":12895,"position":5},"title":"Mechanistic M\u00e9nage \u00e0 trois","author":"Henry Rzepa","date":"November 18, 2009","format":false,"excerpt":"Curly arrow pushing is one of the essential tools of a mechanistic chemist. Many a published article will speculate about the arrow pushing in a mechanism, although it is becoming increasingly common for these speculations to be backed up by quantitative quantum mechanical and dynamical calculations. These have the potential\u2026","rel":"","context":"In "Curly arrows"","block_context":{"text":"Curly arrows","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2327"},"img":{"alt_text":"Oxygen-nitrogen exchange between three nitrosonium cations","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/11\/no-exchange.jpg?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\/12895","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=12895"}],"version-history":[{"count":26,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/12895\/revisions"}],"predecessor-version":[{"id":12957,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/12895\/revisions\/12957"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=12895"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=12895"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=12895"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=12895"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}