{"id":1752,"date":"2019-10-30T11:42:25","date_gmt":"2019-10-30T11:42:25","guid":{"rendered":"http:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/?p=1752"},"modified":"2023-03-31T07:44:09","modified_gmt":"2023-03-31T07:44:09","slug":"synthetic-organic-electrochemistry","status":"publish","type":"post","link":"https:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/2019\/10\/30\/synthetic-organic-electrochemistry\/","title":{"rendered":"Synthetic Organic Electrochemistry"},"content":{"rendered":"\r\n

Electrochemical Generation and Utilization of Alkoxy Radicals<\/h3>\r\n

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This highlight summarises electrochemical approaches for the generation and utilization of alkoxy radicals, predominantly focusing on recent advances (2012-present). The application of electrochemically generated alkoxy radicals in a diverse range of transformations is described, including discussion on reaction mechanisms, scope and limitations, in addition to highlighting future challenges in this burgeoning area of sustainable synthesis. (Chem. Commun.<\/em>, 2023, 59<\/strong>, 3655-3664<\/span>.) [link<\/span><\/a>] [Part of themed collection:\u00a0Chemical Communications Hot Articles 2023]<\/span><\/strong><\/span><\/p>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n

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Deconstructive Functionalization of Unstrained Cycloalkanols via Electrochemically-Generated Aromatic Radical Cations<\/h3>\r\n

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Herein we report an electrochemical approach for the deconstructive functionalization of cycloalkanols, where various alcohols, carboxylic acids, and N-heterocycles are employed as nucleophiles. The method has been demonstrated across a broad range of cycloalkanol substrates, including various ring sizes and substituents, to access useful remotely functionalized ketone products (36 examples). The method was demonstrated on gram-scale via single pass continuous flow, which exhibited increased productivity in relation to the batch process. (<\/span>Org. Lett<\/em>., 2023,\u00a025<\/strong>, 1486-1490). [link<\/a><\/span>]<\/p>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n

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Electrochemical Alkene Azidocyanation\u00a0via<\/em> 1,4-Nitrile Migration<\/h3>\r\n

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An electrochemical method for the azidocyanation of alkenes via 1,4-nitrile migration has been developed. This organic oxidant free method is applicable across various alkene containing cyanohydrins, and provides access to a broad range of synthetically useful 1,2-azidonitriles (28 examples). This methodology was extended to an electrochemical alkene sulfonylcyanation procedure, as well as to access a trifunctionalized hexanenitrile from a malononitrile starting material. The orthogonal derivatization of the products was also demonstrated through chemoselective transformations. (<\/span>Chem. Commun<\/em>., 2022, 58<\/strong>, 8658-8662.) [link<\/a><\/span>]<\/p>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n<\/div>\r\n

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Electrochemical Deconstructive Functionalization of Cycloalkanols via Alkoxy Radicals Enabled by Proton-Coupled Electron Transfer<\/h3>\r\n

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Herein, we report a new electrochemical method for alkoxy radical generation from alcohols using a Proton-Coupled Electron Transfer (PCET) approach, showcased via the deconstructive functionalization of cycloalkanols. The electrochemical method is applicable across a diverse array of substituted cycloalkanols, accessing a broad range of synthetically useful distally func-tionalized ketones. The orthogonal derivatization of the products has been demonstrated through chemoselective transfor-mations, and the electrochemical process has been performed on gram scale in continuous single-pass flow. (Org. Lett<\/em>., 2022, 24<\/strong>, 3890-3895.) [link<\/span><\/a>]<\/p>\r\n

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Electrochemical oxidative Z<\/em>-selective C(sp2)-H chlorination of acrylamides<\/h3>\r\n\r\n\r\n\r\n

An electrochemical method for the oxidative Z<\/em>-selective C(sp2<\/sup>)\u2013H chlorination of acrylamides has been developed. This catalyst and organic oxidant free method is applicable across various substituted tertiary acrylamides, and provides access to a broad range of synthetically useful Z<\/em>–b<\/em>-chloroacrylamides in good yields (22 examples, 73% average yield). The orthogonal derivatization of the products was demonstrated through chemoselective transformations and the electrochemical process was performed on gram scale in flow. (Chem. Commun<\/em>., 2021, 57<\/strong>, 12643-12646). [link<\/a>] [Invited contribution to the 2021 Emerging Investigators themed collection]<\/strong><\/p>\r\n\r\n\r\n\r\n

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Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals<\/h3>\r\n\r\n\r\n\r\n

Alkoxy radicals are highly transient species that exhibit diverse reactivity, including hydrogen atom transfer, addition to pi-systems and beta-scission processes. The generation of alkoxy radicals directly from aliphatic alcohols is challenging, partly due to the high dissociation energy of RO\u2212H bonds (~105 kcal\/mol).<\/p>\r\n\r\n\r\n\r\n

A manganese-catalyzed electrochemical deconstructive chlorination of cycloalkanols has been developed. This electrochemical method provides access to alkoxy radicals from alcohols and exhibits a broad substrate scope, with various cyclopropanols and cyclobutanols converted into synthetically useful beta- and gamma-chlorinated ketones (40 examples). Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on gram scale (Org. Lett.<\/em>, 2019, 21, 9241-9246). [link<\/a>]<\/p>\r\n\r\n\r\n\r\n

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Electrochemical Generation and Utilization of Alkoxy Radicals This highlight summarises electrochemical approaches for the generation and utilization of alkoxy radicals, predominantly focusing on recent advances (2012-present). The application of electrochemically generated alkoxy radicals in a diverse range of transformations is described, including discussion on reaction mechanisms, scope and limitations, in addition to highlighting future challenges […]<\/p>\n","protected":false},"author":623,"featured_media":0,"comment_status":"closed","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_feature_clip_id":0,"_jetpack_memberships_contains_paid_content":false,"footnotes":"","jetpack_post_was_ever_published":false},"categories":[1],"tags":[],"class_list":["post-1752","post","type-post","status-publish","format-standard","hentry","category-uncategorized"],"jetpack_sharing_enabled":true,"meta_box":[],"jetpack_featured_media_url":"","_links":{"self":[{"href":"https:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/wp-json\/wp\/v2\/posts\/1752","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/wp-json\/wp\/v2\/users\/623"}],"replies":[{"embeddable":true,"href":"https:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/wp-json\/wp\/v2\/comments?post=1752"}],"version-history":[{"count":26,"href":"https:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/wp-json\/wp\/v2\/posts\/1752\/revisions"}],"predecessor-version":[{"id":2711,"href":"https:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/wp-json\/wp\/v2\/posts\/1752\/revisions\/2711"}],"wp:attachment":[{"href":"https:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/wp-json\/wp\/v2\/media?parent=1752"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/wp-json\/wp\/v2\/categories?post=1752"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/blogs.cardiff.ac.uk\/themorrillgroup\/wp-json\/wp\/v2\/tags?post=1752"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}