{"id":25415,"date":"2022-08-14T07:16:26","date_gmt":"2022-08-14T06:16:26","guid":{"rendered":"https:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=25415"},"modified":"2022-08-14T07:16:26","modified_gmt":"2022-08-14T06:16:26","slug":"unexpected-isomerization-of-oxetane-carboxylic-acids-substrate-design","status":"publish","type":"post","link":"https:\/\/www.rzepa.net\/blog\/?p=25415","title":{"rendered":"Unexpected Isomerization of Oxetane-Carboxylic Acids \u2013 substrate design."},"content":{"rendered":"
\n

Having established a viable model for the unexpected isomerism of oxetane carboxylic acids to lactones[1]<\/a><\/span>, and taken a look at a variation in the proton transfer catalyst needed to accomplish the transformation, I now investigate the substrate itself.\"\"<\/a><\/p>\n

R’ is set to have three values, R’=H (the original substituent), R’= CH3<\/sub> and R’= CF3<\/sub> (FAIR data DOI: 10.14469\/hpc\/10820<\/a>)<\/p>\n\n\n\n\n\n\n
R’<\/th>\n\u0394G\u2021<\/sup>, kcal\/mol<\/th>\n<\/tr>\n
H<\/th>\n27.0<\/th>\n<\/tr>\n
CH3<\/sub><\/th>\n29.1<\/th>\n<\/tr>\n
CF3<\/sub><\/th>\n39.6<\/th>\n<\/tr>\n<\/tbody>\n<\/table>\n

\"\"<\/p>\n

The inference is clear-cut; to inhibit the isomerisation to a lactone, CF3<\/sub> groups substituted onto the methylene groups of the oxetane will effectively do this, with CH3<\/sub> itself having a much weaker effect.<\/p>\n

\n

DOI: 10.14469\/hpc\/10861 and 10.14469\/hpc\/10862<\/a><\/p>\n

\n

References<\/h2>\n
  1. B. Chalyk, A. Grynyova, K. Filimonova, T.V. Rudenko, D. Dibchak, and P.K. Mykhailiuk, \"Unexpected Isomerization of Oxetane-Carboxylic Acids\", Organic Letters<\/i>, vol. 24, pp. 4722-4728, 2022. https:\/\/doi.org\/10.1021\/acs.orglett.2c01402<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

    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’= CH3 and R’= CF3 (FAIR […]<\/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,"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":[1085],"tags":[],"class_list":["post-25415","post","type-post","status-publish","format-standard","hentry","category-reaction-mechanism-2"],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"","jetpack_sharing_enabled":true,"jetpack_shortlink":"https:\/\/wp.me\/p1gPyz-6BV","jetpack_likes_enabled":true,"_links":{"self":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/posts\/25415","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=25415"}],"version-history":[{"count":0,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/posts\/25415\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=25415"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=25415"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=25415"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}