{"id":25391,"date":"2022-08-13T17:18:41","date_gmt":"2022-08-13T16:18:41","guid":{"rendered":"https:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=25391"},"modified":"2022-09-11T06:16:01","modified_gmt":"2022-09-11T05:16:01","slug":"unexpected-isomerization-of-oxetane-carboxylic-acids-catalyst-design","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25391","title":{"rendered":"Unexpected Isomerization of Oxetane-Carboxylic Acids \u2013 catalyst design."},"content":{"rendered":"<div class=\"kcite-section\" kcite-section-id=\"25391\">\n<p>Previously, a mechanism with a reasonable predicted energy was modelled for the isomerisation of an oxetane carboxylic acid to a lactone by using two further molecules of acid to transfer the proton and in the process encouraging an Sn2 reaction with inversion to open the oxetane ring. <a href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/oxetane1.svg\"><img decoding=\"async\" class=\"alignnone size-full wp-image-25393\" src=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/oxetane1.svg\" alt=\"\" width=\"450\" \/><\/a><\/p>\n<p>We are now ready to explore variations to this mechanism to see what happens. The first hypothesis is that of replacing two carboxylic acids with one molecule with similar properties, the argument being that bringing two acids together decreases their entropy and hence increases the free energy required for the process. If they come pre-joined, this entropic problem is eliminated and the free energy should reduce. Shown below is a small conjugated molecule with the central OHO motif replaced by NCN instead.<\/p>\n<p><a href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/designed.svg\"><img decoding=\"async\" class=\"alignnone size-full wp-image-25394\" src=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/designed.svg\" alt=\"\" width=\"250\" \/><\/a><\/p>\n<p><img decoding=\"async\" class=\"alignnone size-medium wp-image-25397\" src=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/new_catalyst_tot_ener.svg\" alt=\"\" width=\"400\" \/><\/p>\n<p><a href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/new_catalyst_rms_gnorm.svg\"><img decoding=\"async\" class=\"alignnone size-full wp-image-25396\" src=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/new_catalyst_rms_gnorm.svg\" alt=\"\" width=\"400\" \/><\/a><\/p>\n<p><a href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/trimer-3_mol_prop.svg\"><img decoding=\"async\" class=\"alignnone size-full wp-image-25406\" src=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/trimer-3_mol_prop.svg\" alt=\"\" width=\"400\" \/><\/a><\/p>\n<p><img decoding=\"async\" class=\"alignnone size-full wp-image-25400\" src=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/new-catalyst.gif\" alt=\"\" width=\"450\" \/><\/p>\n<p>The activation free energy (\u03c9B97XF\/Def2-TZVPP, FAIR DOI: <a href=\"https:\/\/doi.org\/10.14469\/hpc\/10820\">10.14469\/hpc\/10820<\/a>) is 18.4 kcal\/mol, to be compared to 27.0 when using two carboxylic acids for the transfer. Of course, one would need to optimise the catalyst for many properties, including ease of synthesis, stability, size, isomerism etc, but you get the idea from the procedure here.<\/p>\n<p>The catalyst &#8220;designed&#8221; here is for proton transfer. One has to wonder whether bespoke catalysts of this type might be useful for any reaction where proton transfer is a vital component!<\/p>\n<hr \/>\n<p>DOI: 10.14469\/hpc\/10858 and <a href=\"http:\/\/doi.org\/10.14469\/hpc\/10862\" rel=\"noopener\" target=\"_blank\">10.14469\/hpc\/10862<\/a><\/p>\n<hr \/>\n<!-- kcite active, but no citations found -->\n<\/div> <!-- kcite-section 25391 -->","protected":false},"excerpt":{"rendered":"<p>Previously, a mechanism with a reasonable predicted energy was modelled for the isomerisation of an oxetane carboxylic acid to a lactone by using two further molecules of acid to transfer the proton and in the process encouraging an Sn2 reaction with inversion to open the oxetane ring. We are now ready to explore variations to [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_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},"jetpack_post_was_ever_published":false},"categories":[1086],"tags":[2648],"ppma_author":[2661],"class_list":["post-25391","post","type-post","status-publish","format-standard","hentry","category-reaction-mechanism-2","tag-interesting-chemistry"],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.5 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Unexpected Isomerization of Oxetane-Carboxylic Acids \u2013 catalyst design. - 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=25391\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Unexpected Isomerization of Oxetane-Carboxylic Acids \u2013 catalyst design. - Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"og:description\" content=\"Previously, a mechanism with a reasonable predicted energy was modelled for the isomerisation of an oxetane carboxylic acid to a lactone by using two further molecules of acid to transfer the proton and in the process encouraging an Sn2 reaction with inversion to open the oxetane ring. We are now ready to explore variations to [&hellip;]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25391\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"article:published_time\" content=\"2022-08-13T16:18:41+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2022-09-11T05:16:01+00:00\" \/>\n<meta property=\"og:image\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/oxetane1.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=\"1 minute\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"Unexpected Isomerization of Oxetane-Carboxylic Acids \u2013 catalyst design. - 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=25391","og_locale":"en_GB","og_type":"article","og_title":"Unexpected Isomerization of Oxetane-Carboxylic Acids \u2013 catalyst design. - Henry Rzepa&#039;s Blog","og_description":"Previously, a mechanism with a reasonable predicted energy was modelled for the isomerisation of an oxetane carboxylic acid to a lactone by using two further molecules of acid to transfer the proton and in the process encouraging an Sn2 reaction with inversion to open the oxetane ring. We are now ready to explore variations to [&hellip;]","og_url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25391","og_site_name":"Henry Rzepa&#039;s Blog","article_published_time":"2022-08-13T16:18:41+00:00","article_modified_time":"2022-09-11T05:16:01+00:00","og_image":[{"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/oxetane1.svg","type":"","width":"","height":""}],"author":"Henry Rzepa","twitter_card":"summary_large_image","twitter_misc":{"Written by":"Henry Rzepa","Estimated reading time":"1 minute"},"schema":{"@context":"https:\/\/schema.org","@graph":[{"@type":"Article","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25391#article","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25391"},"author":{"name":"Henry Rzepa","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"headline":"Unexpected Isomerization of Oxetane-Carboxylic Acids \u2013 catalyst design.","datePublished":"2022-08-13T16:18:41+00:00","dateModified":"2022-09-11T05:16:01+00:00","mainEntityOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25391"},"wordCount":226,"commentCount":0,"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25391#primaryimage"},"thumbnailUrl":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/oxetane1.svg","keywords":["Interesting chemistry"],"articleSection":["reaction mechanism"],"inLanguage":"en-GB","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25391#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25391","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25391","name":"Unexpected Isomerization of Oxetane-Carboxylic Acids \u2013 catalyst design. - 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Here I explore alternatives. This first attempt uses a second molecule of a carboxylic acid (modelled as formic acid for\u2026","rel":"","context":"Similar post","block_context":{"text":"Similar post","link":""},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/Rtn.gif?resize=350%2C200&ssl=1","width":350,"height":200,"srcset":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/Rtn.gif?resize=350%2C200&ssl=1 1x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/Rtn.gif?resize=525%2C300&ssl=1 1.5x"},"classes":[]},{"id":25313,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25313","url_meta":{"origin":25391,"position":1},"title":"Unexpected Isomerization of Oxetane-Carboxylic Acids &#8211; 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 &quot;reaction mechanism&quot;","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":25439,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25439","url_meta":{"origin":25391,"position":2},"title":"Unexpected Isomerization of Oxetane-Carboxylic Acids \u2013 an alternative autocatalytic mechanism evaluated.","author":"Henry Rzepa","date":"August 17, 2022","format":false,"excerpt":"Previously, I looked at autocatalytic mechanisms where the carboxyl group of an oxetane-carboxylic acid could catalyse its transformation to a lactone, finding that a chain of two such groups were required to achieve the result. Here I look at an alternative mode where the oxetane-carboxylate itself acts as the transfer\u2026","rel":"","context":"In &quot;reaction mechanism&quot;","block_context":{"text":"reaction mechanism","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1086"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2022\/08\/saddle.gif?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":25415,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25415","url_meta":{"origin":25391,"position":3},"title":"Unexpected Isomerization of Oxetane-Carboxylic Acids \u2013 substrate design.","author":"Henry Rzepa","date":"August 14, 2022","format":false,"excerpt":"Having established a viable model for the unexpected isomerism of oxetane carboxylic acids to lactones, and taken a look at a variation in the proton transfer catalyst needed to accomplish the transformation, I now investigate the substrate itself. R' is set to have three values, R'=H (the original substituent), R'=\u2026","rel":"","context":"In &quot;reaction mechanism&quot;","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":5114,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5114","url_meta":{"origin":25391,"position":4},"title":"Mechanism of the reduction of a carboxylic acid by borane: revisited and revised.","author":"Henry Rzepa","date":"October 16, 2011","format":false,"excerpt":"I asked a while back\u00a0whether blogs could be considered a serious form of scholarly scientific communication (and so has Peter Murray-Rust more recently). A case for doing so might be my post of about a year ago, addressing why borane reduces a carboxylic acid, but not its ester, where I\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":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/10\/acyloxy1-page001.svg","width":350,"height":200},"classes":[]},{"id":18091,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=18091","url_meta":{"origin":25391,"position":5},"title":"The conformation of carboxylic acids revealed.","author":"Henry Rzepa","date":"April 11, 2017","format":false,"excerpt":"Following my conformational exploration of enols, here is one about a much more common molecule, a carboxylic acid. The components of the search are shown as four queries below, which will be combined in various Boolean senses (DOI:\u00a010.14469\/hpc\/2462). Query one defines the carboxylic acid, with 3-coordinate carbon specified at the\u2026","rel":"","context":"In &quot;crystal_structure_mining&quot;","block_context":{"text":"crystal_structure_mining","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1745"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/04\/051-1024x676.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\/25391","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=25391"}],"version-history":[{"count":16,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/25391\/revisions"}],"predecessor-version":[{"id":25437,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/25391\/revisions\/25437"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=25391"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=25391"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=25391"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=25391"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}