Mechanism-Dependent Selectivity: Fluorocyclization of Unsaturated Carboxylic Acids or Alcohols by Hypervalent Iodine
To understand the unprecedented difference between and selectivity in hypervalent iodine (III) promoted fluorocyclization of unsaturated carboxylic acids or alcohols by difluoroiodotoluene, density functional theory (DFT) studies have been performed to systematically compare both the previous propos...
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Published in: | Frontiers in chemistry 2022-05, Vol.10, p.897828-897828 |
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creator | Su, Jiaqi Shu, Siwei Li, Yinwu Chen, Yong Dong, Jinxiang Liu, Yan Fang, Yanxiong Ke, Zhuofeng |
description | To understand the unprecedented difference between
and
selectivity in hypervalent iodine (III) promoted fluorocyclization of unsaturated carboxylic acids or alcohols by difluoroiodotoluene, density functional theory (DFT) studies have been performed to systematically compare both the previous proposed "fluorination first and cyclization later" mechanism and the alternative "cyclization first and fluorination later" mechanism. Our results revealed that the selectivity is mechanism-dependent. The unsaturated alcohol prefers the fluorination first and the
cyclization later pathway, leading to the experimentally observed
ether product. In contrast, the unsaturated carboxylic acid plausibly undergoes the
cyclization first and the fluorination later to the experimentally observed
lactone product. The p
property of the functional group of the substrate is found to play a key role in determining the reaction mechanism. The provided insights into the mechanism-dependent selectivity should help advance the development of fluorocyclization reactions with hypervalent iodine reagents. |
doi_str_mv | 10.3389/fchem.2022.897828 |
format | article |
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and
selectivity in hypervalent iodine (III) promoted fluorocyclization of unsaturated carboxylic acids or alcohols by difluoroiodotoluene, density functional theory (DFT) studies have been performed to systematically compare both the previous proposed "fluorination first and cyclization later" mechanism and the alternative "cyclization first and fluorination later" mechanism. Our results revealed that the selectivity is mechanism-dependent. The unsaturated alcohol prefers the fluorination first and the
cyclization later pathway, leading to the experimentally observed
ether product. In contrast, the unsaturated carboxylic acid plausibly undergoes the
cyclization first and the fluorination later to the experimentally observed
lactone product. The p
property of the functional group of the substrate is found to play a key role in determining the reaction mechanism. The provided insights into the mechanism-dependent selectivity should help advance the development of fluorocyclization reactions with hypervalent iodine reagents.</description><identifier>ISSN: 2296-2646</identifier><identifier>EISSN: 2296-2646</identifier><identifier>DOI: 10.3389/fchem.2022.897828</identifier><identifier>PMID: 35620652</identifier><language>eng</language><publisher>Switzerland: Frontiers Media S.A</publisher><subject>5-oxo ; 6-endo ; Chemistry ; cyclization ; fluorination ; hypervalent iodine ; mechanism</subject><ispartof>Frontiers in chemistry, 2022-05, Vol.10, p.897828-897828</ispartof><rights>Copyright © 2022 Su, Shu, Li, Chen, Dong, Liu, Fang and Ke.</rights><rights>Copyright © 2022 Su, Shu, Li, Chen, Dong, Liu, Fang and Ke. 2022 Su, Shu, Li, Chen, Dong, Liu, Fang and Ke</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c465t-91adadd521265e81095b5d3ae16bede96b4615840ca9b1400904aa588eb3348d3</citedby><cites>FETCH-LOGICAL-c465t-91adadd521265e81095b5d3ae16bede96b4615840ca9b1400904aa588eb3348d3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC9127131/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC9127131/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,723,776,780,881,27903,27904,53769,53771</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/35620652$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Su, Jiaqi</creatorcontrib><creatorcontrib>Shu, Siwei</creatorcontrib><creatorcontrib>Li, Yinwu</creatorcontrib><creatorcontrib>Chen, Yong</creatorcontrib><creatorcontrib>Dong, Jinxiang</creatorcontrib><creatorcontrib>Liu, Yan</creatorcontrib><creatorcontrib>Fang, Yanxiong</creatorcontrib><creatorcontrib>Ke, Zhuofeng</creatorcontrib><title>Mechanism-Dependent Selectivity: Fluorocyclization of Unsaturated Carboxylic Acids or Alcohols by Hypervalent Iodine</title><title>Frontiers in chemistry</title><addtitle>Front Chem</addtitle><description>To understand the unprecedented difference between
and
selectivity in hypervalent iodine (III) promoted fluorocyclization of unsaturated carboxylic acids or alcohols by difluoroiodotoluene, density functional theory (DFT) studies have been performed to systematically compare both the previous proposed "fluorination first and cyclization later" mechanism and the alternative "cyclization first and fluorination later" mechanism. Our results revealed that the selectivity is mechanism-dependent. The unsaturated alcohol prefers the fluorination first and the
cyclization later pathway, leading to the experimentally observed
ether product. In contrast, the unsaturated carboxylic acid plausibly undergoes the
cyclization first and the fluorination later to the experimentally observed
lactone product. The p
property of the functional group of the substrate is found to play a key role in determining the reaction mechanism. The provided insights into the mechanism-dependent selectivity should help advance the development of fluorocyclization reactions with hypervalent iodine reagents.</description><subject>5-oxo</subject><subject>6-endo</subject><subject>Chemistry</subject><subject>cyclization</subject><subject>fluorination</subject><subject>hypervalent iodine</subject><subject>mechanism</subject><issn>2296-2646</issn><issn>2296-2646</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><sourceid>DOA</sourceid><recordid>eNpVkU1v1DAQhiMEolXpD-CCcuSSrb_X5oC02tJ2pSIO0LPl2JOuKydebGdF-PVku6VqT7Y8M8871lNVHzFaUCrVRWe30C8IImQh1VIS-aY6JUSJhggm3r64n1TnOT8ghDDBlBH0vjqhXBAkODmtynewWzP43DeXsIPBwVDqnxDAFr_3ZfpSX4UxpmgnG_xfU3wc6tjVd0M2ZUymgKvXJrXxzxS8rVfWu1zHVK-CjdsYct1O9c20g7Q34UDeROcH-FC960zIcP50nlV3V99-rW-a2x_Xm_XqtrFM8NIobJxxjhNMBAeJkeItd9QAFi04UKJlAnPJkDWqxQwhhZgxXEpoKWXS0bNqc-S6aB70LvnepElH4_XjQ0z32qTibQBNZesQIMkURozQpWFSdC2XVHFEJKMz6-uRtRvbHpydf5NMeAV9XRn8Vt_HvVaYLDHFM-DzEyDF3yPkonufLYRgBohj1kQs506J0CELH1ttijkn6J5jMNIH-fpRvj7I10f588ynl_s9T_xXTf8BtXWtDA</recordid><startdate>20220510</startdate><enddate>20220510</enddate><creator>Su, Jiaqi</creator><creator>Shu, Siwei</creator><creator>Li, Yinwu</creator><creator>Chen, Yong</creator><creator>Dong, Jinxiang</creator><creator>Liu, Yan</creator><creator>Fang, Yanxiong</creator><creator>Ke, Zhuofeng</creator><general>Frontiers Media S.A</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>5PM</scope><scope>DOA</scope></search><sort><creationdate>20220510</creationdate><title>Mechanism-Dependent Selectivity: Fluorocyclization of Unsaturated Carboxylic Acids or Alcohols by Hypervalent Iodine</title><author>Su, Jiaqi ; Shu, Siwei ; Li, Yinwu ; Chen, Yong ; Dong, Jinxiang ; Liu, Yan ; Fang, Yanxiong ; Ke, Zhuofeng</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c465t-91adadd521265e81095b5d3ae16bede96b4615840ca9b1400904aa588eb3348d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>5-oxo</topic><topic>6-endo</topic><topic>Chemistry</topic><topic>cyclization</topic><topic>fluorination</topic><topic>hypervalent iodine</topic><topic>mechanism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Su, Jiaqi</creatorcontrib><creatorcontrib>Shu, Siwei</creatorcontrib><creatorcontrib>Li, Yinwu</creatorcontrib><creatorcontrib>Chen, Yong</creatorcontrib><creatorcontrib>Dong, Jinxiang</creatorcontrib><creatorcontrib>Liu, Yan</creatorcontrib><creatorcontrib>Fang, Yanxiong</creatorcontrib><creatorcontrib>Ke, Zhuofeng</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><collection>DOAJ: Directory of Open Access Journals</collection><jtitle>Frontiers in chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Su, Jiaqi</au><au>Shu, Siwei</au><au>Li, Yinwu</au><au>Chen, Yong</au><au>Dong, Jinxiang</au><au>Liu, Yan</au><au>Fang, Yanxiong</au><au>Ke, Zhuofeng</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mechanism-Dependent Selectivity: Fluorocyclization of Unsaturated Carboxylic Acids or Alcohols by Hypervalent Iodine</atitle><jtitle>Frontiers in chemistry</jtitle><addtitle>Front Chem</addtitle><date>2022-05-10</date><risdate>2022</risdate><volume>10</volume><spage>897828</spage><epage>897828</epage><pages>897828-897828</pages><issn>2296-2646</issn><eissn>2296-2646</eissn><abstract>To understand the unprecedented difference between
and
selectivity in hypervalent iodine (III) promoted fluorocyclization of unsaturated carboxylic acids or alcohols by difluoroiodotoluene, density functional theory (DFT) studies have been performed to systematically compare both the previous proposed "fluorination first and cyclization later" mechanism and the alternative "cyclization first and fluorination later" mechanism. Our results revealed that the selectivity is mechanism-dependent. The unsaturated alcohol prefers the fluorination first and the
cyclization later pathway, leading to the experimentally observed
ether product. In contrast, the unsaturated carboxylic acid plausibly undergoes the
cyclization first and the fluorination later to the experimentally observed
lactone product. The p
property of the functional group of the substrate is found to play a key role in determining the reaction mechanism. The provided insights into the mechanism-dependent selectivity should help advance the development of fluorocyclization reactions with hypervalent iodine reagents.</abstract><cop>Switzerland</cop><pub>Frontiers Media S.A</pub><pmid>35620652</pmid><doi>10.3389/fchem.2022.897828</doi><tpages>1</tpages><oa>free_for_read</oa></addata></record> |
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subjects | 5-oxo 6-endo Chemistry cyclization fluorination hypervalent iodine mechanism |
title | Mechanism-Dependent Selectivity: Fluorocyclization of Unsaturated Carboxylic Acids or Alcohols by Hypervalent Iodine |
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