{"id":10408,"date":"2013-05-11T16:07:41","date_gmt":"2013-05-11T15:07:41","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=10408"},"modified":"2013-05-13T07:39:34","modified_gmt":"2013-05-13T06:39:34","slug":"concerted-14-addition-of-thioacetic-acid-a-requested-reality-check","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10408","title":{"rendered":"Concerted 1,4-addition of thioacetic acid: a (requested) reality check."},"content":{"rendered":"
\n

Lukas, who occasionally comments on this blog, sent me the following challenge. In a recent article[1]<\/a><\/span> he had proposed that the stereochemical outcome (Z<\/strong>) of reaction between a butenal and thioacetic acid as shown below arose by an unusual concerted cycloaddtion involving an S-H bond. He wrote in the article “…this scheme … recommends itself for evaluation by in silico methods<\/em>“. I asked if the answer could be posted here, and he agreed. So here it is.<\/p>\n

\"Click

Click for 3D<\/p><\/div>\n

My initial instinct was that it might prove to be a reaction with “hidden intermediates<\/em>” (for example transfer of the S-H proton onto the oxygen to form a zwitterionic “hidden intermediate”). Well, this is what the computed transition state[2]<\/a><\/span> and the IRC[3]<\/a><\/span> look like.<\/p>\n

\"Lukas\"<\/p>\n

\u00a0\"Lukas\"<\/p>\n

\"LukasG\"<\/p>\n

    \n
  1. For acrolein itself, the forward free-energy barrier \u0394G\u2020<\/sup>298<\/sub> is 25.8 kcal\/mol (\u03c9B97XD\/6-311G(d,p)\/SCRF=acetone) and the reverse barrier 27.7 kcal\/mol, which makes the overall free energy for the reaction -1.8 kcal\/mol. These values are not inconsistent with an equilibrium thermal reaction at room temperatures or above.<\/span><\/li>\n
  2. The gradients show no sign of any “hidden intermediates”. The reaction indeed is nicely concerted, albeit with O-H bond formation asynchronously preceding that of C-S. This reaction should indeed be added to the pantheon of facile pericyclic (or pseudopericyclic) reaction types.<\/li>\n
  3. For the methyl substituted system (R=Me) the forward barrier is a little lower than before (23.8 kcal\/mol)[4]<\/a><\/span> and the reverse likewise (25.5).\u2021<\/sup> The (Z) product far dominates the (E) (61:1).\u00a0The IRC[5]<\/a><\/span> is similar to the unsubstituted reaction, but with the faintest of hints of a hidden intermediate (at IRC ~0.8).<\/li>\n<\/ol>\n

    \"Lukas_mea\"<\/p>\n

    \"Lukas_me\"\"Lukas_meG\"<\/p>\n

    The reaction itself is a smaller-ring thia-homologue of one reported by Birney[6]<\/a><\/span> and classified there as a pseudopericyclic reaction, the point of interest being the difference in behaviour between the O-H acid and the S-H acid.\"birney\"<\/p>\n

    Well, that is the in silico<\/em> counterpart to the in silica<\/em> experiment. It took a few hours (about the same as a few NMR measurements?).<\/p>\n

    \n

    \u2021<\/sup>Slightly lower values are obtained for the s-cis<\/i> conformation[7]<\/a><\/span> of the thio-acid:\u00a0\u0394G\u2020<\/sup>298<\/sub>\u00a0is 21.0 kcal\/mol for the forward and 22.0 for the reverse reactions.<\/p>\n

    \n

    References<\/h2>\n
    1. L. Hintermann, and A. Turo\u010dkin, \"Reversible Generation of Metastable Enols in the 1,4-Addition of Thioacetic Acid to \u03b1,\u03b2-Unsaturated Carbonyl Compounds\", The Journal of Organic Chemistry<\/i>, vol. 77, pp. 11345-11348, 2012. https:\/\/doi.org\/10.1021\/jo3021709<\/a>\n\n<\/li>\n
    2. H.S. Rzepa, \"Gaussian Job Archive for C5H8O2S\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.701466<\/a>\n\n<\/li>\n
    3. H.S. Rzepa, \"Gaussian Job Archive for C5H8O2S\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.701174<\/a>\n\n<\/li>\n
    4. H.S. Rzepa, \"Gaussian Job Archive for C6H10O2S\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.701467<\/a>\n\n<\/li>\n
    5. H.S. Rzepa, \"Gaussian Job Archive for C6H10O2S\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.701468<\/a>\n\n<\/li>\n
    6. H. Ji, L. Li, X. Xu, S. Ham, L.A. Hammad, and D.M. Birney*, \"Multiphoton Infrared Initiated Thermal Reactions of Esters: Pseudopericyclic Eight-Centered<i>cis<\/i>-Elimination\", Journal of the American Chemical Society<\/i>, vol. 131, pp. 528-537, 2008. https:\/\/doi.org\/10.1021\/ja804812c<\/a>\n\n<\/li>\n
    7. H.S. Rzepa, \"Gaussian Job Archive for C6H10O2S\", 2013. https:\/\/doi.org\/10.6084\/m9.figshare.701501<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

      Lukas, who occasionally comments on this blog, sent me the following challenge. In a recent article he had proposed that the stereochemical outcome (Z) of reaction between a butenal and thioacetic acid as shown below arose by an unusual concerted cycloaddtion involving an S-H bond. He wrote in the article “…this scheme … recommends itself […]<\/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":[4],"tags":[843],"ppma_author":[2661],"class_list":["post-10408","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry","tag-reaction-mechanism"],"yoast_head":"\nConcerted 1,4-addition of thioacetic acid: a (requested) reality check. - 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=10408\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Concerted 1,4-addition of thioacetic acid: a (requested) reality check. - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"Lukas, who occasionally comments on this blog, sent me the following challenge. In a recent article he had proposed that the stereochemical outcome (Z) of reaction between a butenal and thioacetic acid as shown below arose by an unusual concerted cycloaddtion involving an S-H bond. He wrote in the article “…this scheme … recommends itself […]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10408\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa's Blog\" \/>\n<meta property=\"article:published_time\" content=\"2013-05-11T15:07:41+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2013-05-13T06:39:34+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/05\/Bildschirmfoto-2013-05-09-um-21.10.33.png\" \/>\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":"Concerted 1,4-addition of thioacetic acid: a (requested) reality check. - 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=10408","og_locale":"en_GB","og_type":"article","og_title":"Concerted 1,4-addition of thioacetic acid: a (requested) reality check. - Henry Rzepa's Blog","og_description":"Lukas, who occasionally comments on this blog, sent me the following challenge. In a recent article he had proposed that the stereochemical outcome (Z) of reaction between a butenal and thioacetic acid as shown below arose by an unusual concerted cycloaddtion involving an S-H bond. 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He wrote \"\u00a0I don't understand why the system should prefer to go via fragmentation-recombination (... the evidence being that\u00a0oxygen labelling shows scrambling)\u00a0when there is an easy concerted pathway available (...\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":"Boek1","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/06\/Boek1.gif?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":25313,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25313","url_meta":{"origin":10408,"position":1},"title":"Unexpected Isomerization of Oxetane-Carboxylic Acids – a first look at the mechanism","author":"Henry Rzepa","date":"August 7, 2022","format":false,"excerpt":"Derek Lowe's blog has a recent post entitled A Downside to Oxetane Acids which picks up on a recent article describing how these acids are unexpectedly unstable, isomerising to a lactone at a significant rate without the apparent need for any catalyst. This is important because these types of compound\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":"","src":"","width":0,"height":0},"classes":[]},{"id":11065,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=11065","url_meta":{"origin":10408,"position":2},"title":"Experimental evidence for “hidden intermediates”? Epoxidation of ethene by peracid.","author":"Henry Rzepa","date":"August 25, 2013","format":false,"excerpt":"The concept of a \"hidden intermediate\" in a reaction pathway has been promoted by Dieter Cremer and much invoked on this blog. When I used this term in a recent article of ours, a referee tried to object, saying it was not in common use in chemistry. The term clearly\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":"peracid+alkene1","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/08\/peracid%2Balkene1.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":15295,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=15295","url_meta":{"origin":10408,"position":3},"title":"I\u2019ve started so I\u2019ll finish. Mechanism and kinetic isotope effects for protiodecarboxylation of indoles.","author":"Henry Rzepa","date":"January 2, 2016","format":false,"excerpt":"Another mechanistic study we\u00a0started in\u00a01972 is\u00a0here 40+ years on\u00a0subjected to quantum mechanical scrutiny. The kinetics are again complex, the mechanism involving protonation\u2021 of the indole carboxylate (by a general acid), followed by the presumption of a zwitterionic Wheland intermediate that then loses carbon dioxide in a second step (blue arrows).\u2026","rel":"","context":"In "Historical"","block_context":{"text":"Historical","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=565"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":10015,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10015","url_meta":{"origin":10408,"position":4},"title":"A sideways look at the mechanism of ester hydrolysis.","author":"Henry Rzepa","date":"March 29, 2013","format":false,"excerpt":"The mechanism of ester hydrolysis is a staple of examination questions in organic chemistry. To get a good grade, one might have to reproduce something like the below. Here, I subject that answer to a reality check. In this scheme, HA is a general acid, R=Me, and the net result\u2026","rel":"","context":"In \"ALSO\"","block_context":{"text":"ALSO","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?tag=also"},"img":{"alt_text":"acyl-ester","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/03\/acyl-ester.gif?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":10184,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10184","url_meta":{"origin":10408,"position":5},"title":"Intermediates in oxime formation from hydroxylamine and propanone: now you see them, now you don’t.","author":"Henry Rzepa","date":"April 14, 2013","format":false,"excerpt":"A recent theme here has been to subject to scrutiny well-known mechanisms supposedly involving intermediates. These transients can often involve the creation\/annihilation of charge separation resulting from \u00a0proton transfers, something that a cyclic mechanism can avoid. Here I revisit the formation of an oxime from hydroxylamine and propanone, but with\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":"N-pre","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/04\/N-pre.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\/10408","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=10408"}],"version-history":[{"count":28,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/10408\/revisions"}],"predecessor-version":[{"id":10442,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/10408\/revisions\/10442"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=10408"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=10408"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=10408"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=10408"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}