A Desilylative Approach to Alkyl Substituted C(1)‐Ammonium Enolates: Application in Enantioselective [2+2] Cycloadditions
The catalytic generation of C(1)‐ammonium enolates from the corresponding α‐silyl‐α‐alkyl substituted carboxylic acids using the isothiourea HyperBTM is reported. This desilylative approach grants access to α‐unsubstituted and α‐alkyl substituted C(1)‐ammonium enolates, which are typically difficult...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2022-09, Vol.61 (38), p.e202208800-n/a |
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| creator | Wang, Yihong Young, Claire M. Liu, Honglei Hartley, Will C. Wienhold, Max Cordes, David. B. Slawin, Alexandra M. Z. Smith, Andrew D. |
| description | The catalytic generation of C(1)‐ammonium enolates from the corresponding α‐silyl‐α‐alkyl substituted carboxylic acids using the isothiourea HyperBTM is reported. This desilylative approach grants access to α‐unsubstituted and α‐alkyl substituted C(1)‐ammonium enolates, which are typically difficult to access through traditional methods reliant upon deprotonation. The scope and limitations of this process is established in enantioselective [2+2]‐cycloaddition processes with perfluoroalkylketones (31 examples, up to 96 % yield and >99 : 1 er), as well as selective [2+2]‐cycloaddition with trifluoromethyl enones (4 examples, up to 75 % yield and >99 : 1 er). Preliminary mechanistic studies indicate this process proceeds through an initial kinetic resolution of an in situ prepared (±)‐α‐silyl‐α‐alkyl substituted anhydride, while the reaction process exhibits overall pseudo zero‐order kinetics.
The catalytic generation of unsubstituted and alkyl substituted C(1)‐ammonium enolates from α‐silyl‐α‐alkyl substituted carboxylic acids using the isothiourea HyperBTM has been developed and applied in enantioselective [2+2]‐cycloaddition reactions. |
| doi_str_mv | 10.1002/anie.202208800 |
| format | Article |
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The catalytic generation of unsubstituted and alkyl substituted C(1)‐ammonium enolates from α‐silyl‐α‐alkyl substituted carboxylic acids using the isothiourea HyperBTM has been developed and applied in enantioselective [2+2]‐cycloaddition reactions.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202208800</identifier><identifier>PMID: 35833471</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Ammonium ; Carboxylic acids ; Cycloaddition ; Desilylation ; Enantiomers ; Enolate ; Isothiourea ; Substitutes ; β-Lactone</subject><ispartof>Angewandte Chemie International Edition, 2022-09, Vol.61 (38), p.e202208800-n/a</ispartof><rights>2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH</rights><rights>2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.</rights><rights>2022. This article is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3800-e6df7cdb3a4bccf3de877bf7982466e6a7c933d0e0a1c60ac5088384581d73853</citedby><cites>FETCH-LOGICAL-c3800-e6df7cdb3a4bccf3de877bf7982466e6a7c933d0e0a1c60ac5088384581d73853</cites><orcidid>0000-0002-2104-7313</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.202208800$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202208800$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/35833471$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Wang, Yihong</creatorcontrib><creatorcontrib>Young, Claire M.</creatorcontrib><creatorcontrib>Liu, Honglei</creatorcontrib><creatorcontrib>Hartley, Will C.</creatorcontrib><creatorcontrib>Wienhold, Max</creatorcontrib><creatorcontrib>Cordes, David. B.</creatorcontrib><creatorcontrib>Slawin, Alexandra M. Z.</creatorcontrib><creatorcontrib>Smith, Andrew D.</creatorcontrib><title>A Desilylative Approach to Alkyl Substituted C(1)‐Ammonium Enolates: Application in Enantioselective [2+2] Cycloadditions</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>The catalytic generation of C(1)‐ammonium enolates from the corresponding α‐silyl‐α‐alkyl substituted carboxylic acids using the isothiourea HyperBTM is reported. This desilylative approach grants access to α‐unsubstituted and α‐alkyl substituted C(1)‐ammonium enolates, which are typically difficult to access through traditional methods reliant upon deprotonation. The scope and limitations of this process is established in enantioselective [2+2]‐cycloaddition processes with perfluoroalkylketones (31 examples, up to 96 % yield and >99 : 1 er), as well as selective [2+2]‐cycloaddition with trifluoromethyl enones (4 examples, up to 75 % yield and >99 : 1 er). Preliminary mechanistic studies indicate this process proceeds through an initial kinetic resolution of an in situ prepared (±)‐α‐silyl‐α‐alkyl substituted anhydride, while the reaction process exhibits overall pseudo zero‐order kinetics.
The catalytic generation of unsubstituted and alkyl substituted C(1)‐ammonium enolates from α‐silyl‐α‐alkyl substituted carboxylic acids using the isothiourea HyperBTM has been developed and applied in enantioselective [2+2]‐cycloaddition reactions.</description><subject>Ammonium</subject><subject>Carboxylic acids</subject><subject>Cycloaddition</subject><subject>Desilylation</subject><subject>Enantiomers</subject><subject>Enolate</subject><subject>Isothiourea</subject><subject>Substitutes</subject><subject>β-Lactone</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqFkMtKxDAUhoMoOo5uXUrAjSIdc2mbjLsyjhcYdKGuREqapJgxbcemVYobH8Fn9ElMHS9LVzmQ7_8O5wdgB6MRRogcidLoEUGEIM4RWgEDHBEcUMboqp9DSgPGI7wBNp2be95D8TrYoBGnNGR4AF4TeKKdsZ0VjXnWMFks6krIB9hUMLGPnYXXbeYa07SNVnCyjw8-3t6ToqhK0xZwWlY-p91xn7NGekdVQlP6D1H62Wmr5Zf3jhySezjppK2EUqbn3BZYy4V1evv7HYLb0-nN5DyYXZ1dTJJZIKm_KdCxyplUGRVhJmVOleaMZTkbcxLGsY4Fk2NKFdJIYBkjISPfBeVhxLFilEd0CPaWXn_aU6tdk86rti79ypQwTBjDKOqp0ZKSdeVcrfN0UZtC1F2KUdp3nfZdp79d-8Dut7bNCq1-8Z9yPTBeAi_G6u4fXZpcXkz_5J9Of4xg</recordid><startdate>20220919</startdate><enddate>20220919</enddate><creator>Wang, Yihong</creator><creator>Young, Claire M.</creator><creator>Liu, Honglei</creator><creator>Hartley, Will C.</creator><creator>Wienhold, Max</creator><creator>Cordes, David. B.</creator><creator>Slawin, Alexandra M. Z.</creator><creator>Smith, Andrew D.</creator><general>Wiley Subscription Services, Inc</general><scope>24P</scope><scope>WIN</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><orcidid>https://orcid.org/0000-0002-2104-7313</orcidid></search><sort><creationdate>20220919</creationdate><title>A Desilylative Approach to Alkyl Substituted C(1)‐Ammonium Enolates: Application in Enantioselective [2+2] Cycloadditions</title><author>Wang, Yihong ; Young, Claire M. ; Liu, Honglei ; Hartley, Will C. ; Wienhold, Max ; Cordes, David. B. ; Slawin, Alexandra M. Z. ; Smith, Andrew D.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3800-e6df7cdb3a4bccf3de877bf7982466e6a7c933d0e0a1c60ac5088384581d73853</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Ammonium</topic><topic>Carboxylic acids</topic><topic>Cycloaddition</topic><topic>Desilylation</topic><topic>Enantiomers</topic><topic>Enolate</topic><topic>Isothiourea</topic><topic>Substitutes</topic><topic>β-Lactone</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Wang, Yihong</creatorcontrib><creatorcontrib>Young, Claire M.</creatorcontrib><creatorcontrib>Liu, Honglei</creatorcontrib><creatorcontrib>Hartley, Will C.</creatorcontrib><creatorcontrib>Wienhold, Max</creatorcontrib><creatorcontrib>Cordes, David. B.</creatorcontrib><creatorcontrib>Slawin, Alexandra M. Z.</creatorcontrib><creatorcontrib>Smith, Andrew D.</creatorcontrib><collection>Wiley Online Library (Open Access Collection)</collection><collection>Wiley Online Library (Open Access Collection)</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Wang, Yihong</au><au>Young, Claire M.</au><au>Liu, Honglei</au><au>Hartley, Will C.</au><au>Wienhold, Max</au><au>Cordes, David. B.</au><au>Slawin, Alexandra M. Z.</au><au>Smith, Andrew D.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Desilylative Approach to Alkyl Substituted C(1)‐Ammonium Enolates: Application in Enantioselective [2+2] Cycloadditions</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2022-09-19</date><risdate>2022</risdate><volume>61</volume><issue>38</issue><spage>e202208800</spage><epage>n/a</epage><pages>e202208800-n/a</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>The catalytic generation of C(1)‐ammonium enolates from the corresponding α‐silyl‐α‐alkyl substituted carboxylic acids using the isothiourea HyperBTM is reported. This desilylative approach grants access to α‐unsubstituted and α‐alkyl substituted C(1)‐ammonium enolates, which are typically difficult to access through traditional methods reliant upon deprotonation. The scope and limitations of this process is established in enantioselective [2+2]‐cycloaddition processes with perfluoroalkylketones (31 examples, up to 96 % yield and >99 : 1 er), as well as selective [2+2]‐cycloaddition with trifluoromethyl enones (4 examples, up to 75 % yield and >99 : 1 er). Preliminary mechanistic studies indicate this process proceeds through an initial kinetic resolution of an in situ prepared (±)‐α‐silyl‐α‐alkyl substituted anhydride, while the reaction process exhibits overall pseudo zero‐order kinetics.
The catalytic generation of unsubstituted and alkyl substituted C(1)‐ammonium enolates from α‐silyl‐α‐alkyl substituted carboxylic acids using the isothiourea HyperBTM has been developed and applied in enantioselective [2+2]‐cycloaddition reactions.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>35833471</pmid><doi>10.1002/anie.202208800</doi><tpages>8</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-2104-7313</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Ammonium Carboxylic acids Cycloaddition Desilylation Enantiomers Enolate Isothiourea Substitutes β-Lactone |
| title | A Desilylative Approach to Alkyl Substituted C(1)‐Ammonium Enolates: Application in Enantioselective [2+2] Cycloadditions |
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