Loading…
Atom-economic and stereoselective catalytic synthesis of fully substituted enol esters/carbonates of amides in acyclic systems enabled by boron Lewis acid catalysis
Carboacyloxylation of internal alkynes is emerging as a powerful and straightforward strategy for enol ester synthesis. However, the reported examples come with limitations, including the utilization of noble metal catalysts, the control of regio- and Z / E selectivity, and an application in the syn...
Saved in:
| Published in: | Chemical science (Cambridge) 2023-05, Vol.14 (21), p.568-5618 |
|---|---|
| Main Authors: | , , , , , , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| cited_by | cdi_FETCH-LOGICAL-c429t-42f47afba6c133de07bb818c758bb6e911df2145d3b1b60810d70acb5b73ddd03 |
|---|---|
| cites | cdi_FETCH-LOGICAL-c429t-42f47afba6c133de07bb818c758bb6e911df2145d3b1b60810d70acb5b73ddd03 |
| container_end_page | 5618 |
| container_issue | 21 |
| container_start_page | 568 |
| container_title | Chemical science (Cambridge) |
| container_volume | 14 |
| creator | Xiao, Yuanjiu Tang, Lei Xu, Tong-Tong Sheng, Jiang-Yi-Hui Zhou, Zhongyan Yue, Lei Wang, Guoqiang Oestreich, Martin Feng, Jian-Jun |
| description | Carboacyloxylation of internal alkynes is emerging as a powerful and straightforward strategy for enol ester synthesis. However, the reported examples come with limitations, including the utilization of noble metal catalysts, the control of regio- and
Z
/
E
selectivity, and an application in the synthesis of enol carbonates. Herein, a boron Lewis acid-catalyzed intermolecular carboacyloxylation of ynamides with esters to access fully substituted acyclic enol esters in high yield with generally high
Z
/
E
selectivity (up to >96 : 4) is reported. Most importantly, readily available allylic carbonates are also compatible with this difunctionalization reaction, representing an atom-economic, catalytic and stereoselective protocol for the construction of acyclic β,β-disubstituted enol carbonates of amides for the first time. The application of the carboacyloxylation products to decarboxylative allylations provided a ready access to enantioenriched α-quaternary amides. Moreover, experimental studies and theoretical calculations were performed to illustrate the reaction mechanism and rationalize the stereochemistry.
A boron Lewis acid catalyzes trans-carboacyloxylations of ynamides with esters to afford fully substituted acyclic enol esters/carbonates in high yields and with excellent stereocontrol. |
| doi_str_mv | 10.1039/d3sc01394d |
| format | article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_10231430</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2820965872</sourcerecordid><originalsourceid>FETCH-LOGICAL-c429t-42f47afba6c133de07bb818c758bb6e911df2145d3b1b60810d70acb5b73ddd03</originalsourceid><addsrcrecordid>eNpdkklrVTEUx4Motrx2414JuBHhthnuuJLy6gQPuqiuQ4ZzbUpuUpPcyv0-flDzBp9DNjlwfud_RoReUHJBCR8uDU-aUD7U5gk6ZaSmVdvw4enRZuQEnad0T8rjnDase45OeMfapmP8FP28ymGqQAcfJqux9AanDBFCAgc620fAWmbplly8afH5DpJNOIx4nJ1bcJpVyjbPGQwGHxyGbXi61DKq4GWGHSsna4plPZZ60W4nVbgplRipXIlVC1YhBo838KPoS23NIXFJd4aejdIlOD_8K_T1w_sv60_V5ubj5_XVptI1G3JVs7Hu5KhkqynnBkinVE973TW9Ui0MlJqR0boxXFHVkp4S0xGpVaM6bowhfIXe7XUfZjWB0eBzlE48RDvJuIggrfjX4-2d-BYeBSWM05pvFd4cFGL4PpdZiMkmDc5JD2FOgvWMleE3jBb09X_ofZijL_1tKTK0TV82tEJv95SOIaUI47EaSsT2AMQ1v13vDuC6wK_-rv-I_l53AV7ugZj00fvngvgvDpW6Hw</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2820965872</pqid></control><display><type>article</type><title>Atom-economic and stereoselective catalytic synthesis of fully substituted enol esters/carbonates of amides in acyclic systems enabled by boron Lewis acid catalysis</title><source>PubMed Central</source><creator>Xiao, Yuanjiu ; Tang, Lei ; Xu, Tong-Tong ; Sheng, Jiang-Yi-Hui ; Zhou, Zhongyan ; Yue, Lei ; Wang, Guoqiang ; Oestreich, Martin ; Feng, Jian-Jun</creator><creatorcontrib>Xiao, Yuanjiu ; Tang, Lei ; Xu, Tong-Tong ; Sheng, Jiang-Yi-Hui ; Zhou, Zhongyan ; Yue, Lei ; Wang, Guoqiang ; Oestreich, Martin ; Feng, Jian-Jun</creatorcontrib><description>Carboacyloxylation of internal alkynes is emerging as a powerful and straightforward strategy for enol ester synthesis. However, the reported examples come with limitations, including the utilization of noble metal catalysts, the control of regio- and
Z
/
E
selectivity, and an application in the synthesis of enol carbonates. Herein, a boron Lewis acid-catalyzed intermolecular carboacyloxylation of ynamides with esters to access fully substituted acyclic enol esters in high yield with generally high
Z
/
E
selectivity (up to >96 : 4) is reported. Most importantly, readily available allylic carbonates are also compatible with this difunctionalization reaction, representing an atom-economic, catalytic and stereoselective protocol for the construction of acyclic β,β-disubstituted enol carbonates of amides for the first time. The application of the carboacyloxylation products to decarboxylative allylations provided a ready access to enantioenriched α-quaternary amides. Moreover, experimental studies and theoretical calculations were performed to illustrate the reaction mechanism and rationalize the stereochemistry.
A boron Lewis acid catalyzes trans-carboacyloxylations of ynamides with esters to afford fully substituted acyclic enol esters/carbonates in high yields and with excellent stereocontrol.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/d3sc01394d</identifier><identifier>PMID: 37265723</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Alkynes ; Amides ; Boron ; Carbonates ; Catalysis ; Chemical synthesis ; Chemistry ; Esters ; Lewis acid ; Noble metals ; Reaction mechanisms ; Stereochemistry ; Stereoselectivity ; Substitutes</subject><ispartof>Chemical science (Cambridge), 2023-05, Vol.14 (21), p.568-5618</ispartof><rights>This journal is © The Royal Society of Chemistry.</rights><rights>Copyright Royal Society of Chemistry 2023</rights><rights>This journal is © The Royal Society of Chemistry 2023 The Royal Society of Chemistry</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c429t-42f47afba6c133de07bb818c758bb6e911df2145d3b1b60810d70acb5b73ddd03</citedby><cites>FETCH-LOGICAL-c429t-42f47afba6c133de07bb818c758bb6e911df2145d3b1b60810d70acb5b73ddd03</cites><orcidid>0000-0001-7091-3460 ; 0000-0001-5155-9099 ; 0000-0002-0766-6572 ; 0000-0001-9666-1919 ; 0000-0002-1487-9218 ; 0000-0002-6094-3268</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC10231430/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC10231430/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,315,733,786,790,891,27957,27958,53827,53829</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/37265723$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Xiao, Yuanjiu</creatorcontrib><creatorcontrib>Tang, Lei</creatorcontrib><creatorcontrib>Xu, Tong-Tong</creatorcontrib><creatorcontrib>Sheng, Jiang-Yi-Hui</creatorcontrib><creatorcontrib>Zhou, Zhongyan</creatorcontrib><creatorcontrib>Yue, Lei</creatorcontrib><creatorcontrib>Wang, Guoqiang</creatorcontrib><creatorcontrib>Oestreich, Martin</creatorcontrib><creatorcontrib>Feng, Jian-Jun</creatorcontrib><title>Atom-economic and stereoselective catalytic synthesis of fully substituted enol esters/carbonates of amides in acyclic systems enabled by boron Lewis acid catalysis</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description>Carboacyloxylation of internal alkynes is emerging as a powerful and straightforward strategy for enol ester synthesis. However, the reported examples come with limitations, including the utilization of noble metal catalysts, the control of regio- and
Z
/
E
selectivity, and an application in the synthesis of enol carbonates. Herein, a boron Lewis acid-catalyzed intermolecular carboacyloxylation of ynamides with esters to access fully substituted acyclic enol esters in high yield with generally high
Z
/
E
selectivity (up to >96 : 4) is reported. Most importantly, readily available allylic carbonates are also compatible with this difunctionalization reaction, representing an atom-economic, catalytic and stereoselective protocol for the construction of acyclic β,β-disubstituted enol carbonates of amides for the first time. The application of the carboacyloxylation products to decarboxylative allylations provided a ready access to enantioenriched α-quaternary amides. Moreover, experimental studies and theoretical calculations were performed to illustrate the reaction mechanism and rationalize the stereochemistry.
A boron Lewis acid catalyzes trans-carboacyloxylations of ynamides with esters to afford fully substituted acyclic enol esters/carbonates in high yields and with excellent stereocontrol.</description><subject>Alkynes</subject><subject>Amides</subject><subject>Boron</subject><subject>Carbonates</subject><subject>Catalysis</subject><subject>Chemical synthesis</subject><subject>Chemistry</subject><subject>Esters</subject><subject>Lewis acid</subject><subject>Noble metals</subject><subject>Reaction mechanisms</subject><subject>Stereochemistry</subject><subject>Stereoselectivity</subject><subject>Substitutes</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNpdkklrVTEUx4Motrx2414JuBHhthnuuJLy6gQPuqiuQ4ZzbUpuUpPcyv0-flDzBp9DNjlwfud_RoReUHJBCR8uDU-aUD7U5gk6ZaSmVdvw4enRZuQEnad0T8rjnDase45OeMfapmP8FP28ymGqQAcfJqux9AanDBFCAgc620fAWmbplly8afH5DpJNOIx4nJ1bcJpVyjbPGQwGHxyGbXi61DKq4GWGHSsna4plPZZ60W4nVbgplRipXIlVC1YhBo838KPoS23NIXFJd4aejdIlOD_8K_T1w_sv60_V5ubj5_XVptI1G3JVs7Hu5KhkqynnBkinVE973TW9Ui0MlJqR0boxXFHVkp4S0xGpVaM6bowhfIXe7XUfZjWB0eBzlE48RDvJuIggrfjX4-2d-BYeBSWM05pvFd4cFGL4PpdZiMkmDc5JD2FOgvWMleE3jBb09X_ofZijL_1tKTK0TV82tEJv95SOIaUI47EaSsT2AMQ1v13vDuC6wK_-rv-I_l53AV7ugZj00fvngvgvDpW6Hw</recordid><startdate>20230531</startdate><enddate>20230531</enddate><creator>Xiao, Yuanjiu</creator><creator>Tang, Lei</creator><creator>Xu, Tong-Tong</creator><creator>Sheng, Jiang-Yi-Hui</creator><creator>Zhou, Zhongyan</creator><creator>Yue, Lei</creator><creator>Wang, Guoqiang</creator><creator>Oestreich, Martin</creator><creator>Feng, Jian-Jun</creator><general>Royal Society of Chemistry</general><general>The Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0001-7091-3460</orcidid><orcidid>https://orcid.org/0000-0001-5155-9099</orcidid><orcidid>https://orcid.org/0000-0002-0766-6572</orcidid><orcidid>https://orcid.org/0000-0001-9666-1919</orcidid><orcidid>https://orcid.org/0000-0002-1487-9218</orcidid><orcidid>https://orcid.org/0000-0002-6094-3268</orcidid></search><sort><creationdate>20230531</creationdate><title>Atom-economic and stereoselective catalytic synthesis of fully substituted enol esters/carbonates of amides in acyclic systems enabled by boron Lewis acid catalysis</title><author>Xiao, Yuanjiu ; Tang, Lei ; Xu, Tong-Tong ; Sheng, Jiang-Yi-Hui ; Zhou, Zhongyan ; Yue, Lei ; Wang, Guoqiang ; Oestreich, Martin ; Feng, Jian-Jun</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c429t-42f47afba6c133de07bb818c758bb6e911df2145d3b1b60810d70acb5b73ddd03</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Alkynes</topic><topic>Amides</topic><topic>Boron</topic><topic>Carbonates</topic><topic>Catalysis</topic><topic>Chemical synthesis</topic><topic>Chemistry</topic><topic>Esters</topic><topic>Lewis acid</topic><topic>Noble metals</topic><topic>Reaction mechanisms</topic><topic>Stereochemistry</topic><topic>Stereoselectivity</topic><topic>Substitutes</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Xiao, Yuanjiu</creatorcontrib><creatorcontrib>Tang, Lei</creatorcontrib><creatorcontrib>Xu, Tong-Tong</creatorcontrib><creatorcontrib>Sheng, Jiang-Yi-Hui</creatorcontrib><creatorcontrib>Zhou, Zhongyan</creatorcontrib><creatorcontrib>Yue, Lei</creatorcontrib><creatorcontrib>Wang, Guoqiang</creatorcontrib><creatorcontrib>Oestreich, Martin</creatorcontrib><creatorcontrib>Feng, Jian-Jun</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Xiao, Yuanjiu</au><au>Tang, Lei</au><au>Xu, Tong-Tong</au><au>Sheng, Jiang-Yi-Hui</au><au>Zhou, Zhongyan</au><au>Yue, Lei</au><au>Wang, Guoqiang</au><au>Oestreich, Martin</au><au>Feng, Jian-Jun</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Atom-economic and stereoselective catalytic synthesis of fully substituted enol esters/carbonates of amides in acyclic systems enabled by boron Lewis acid catalysis</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2023-05-31</date><risdate>2023</risdate><volume>14</volume><issue>21</issue><spage>568</spage><epage>5618</epage><pages>568-5618</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><notes>For ESI and crystallographic data in CIF or other electronic format see DOI</notes><notes>2236734</notes><notes>https://doi.org/10.1039/d3sc01394d</notes><notes>2236736</notes><notes>and</notes><notes>Electronic supplementary information (ESI) available: Experimental details, characterization, and spectroscopic data. CCDC</notes><notes>ObjectType-Article-1</notes><notes>SourceType-Scholarly Journals-1</notes><notes>ObjectType-Feature-2</notes><notes>content type line 23</notes><abstract>Carboacyloxylation of internal alkynes is emerging as a powerful and straightforward strategy for enol ester synthesis. However, the reported examples come with limitations, including the utilization of noble metal catalysts, the control of regio- and
Z
/
E
selectivity, and an application in the synthesis of enol carbonates. Herein, a boron Lewis acid-catalyzed intermolecular carboacyloxylation of ynamides with esters to access fully substituted acyclic enol esters in high yield with generally high
Z
/
E
selectivity (up to >96 : 4) is reported. Most importantly, readily available allylic carbonates are also compatible with this difunctionalization reaction, representing an atom-economic, catalytic and stereoselective protocol for the construction of acyclic β,β-disubstituted enol carbonates of amides for the first time. The application of the carboacyloxylation products to decarboxylative allylations provided a ready access to enantioenriched α-quaternary amides. Moreover, experimental studies and theoretical calculations were performed to illustrate the reaction mechanism and rationalize the stereochemistry.
A boron Lewis acid catalyzes trans-carboacyloxylations of ynamides with esters to afford fully substituted acyclic enol esters/carbonates in high yields and with excellent stereocontrol.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>37265723</pmid><doi>10.1039/d3sc01394d</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0001-7091-3460</orcidid><orcidid>https://orcid.org/0000-0001-5155-9099</orcidid><orcidid>https://orcid.org/0000-0002-0766-6572</orcidid><orcidid>https://orcid.org/0000-0001-9666-1919</orcidid><orcidid>https://orcid.org/0000-0002-1487-9218</orcidid><orcidid>https://orcid.org/0000-0002-6094-3268</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 2041-6520 |
| ispartof | Chemical science (Cambridge), 2023-05, Vol.14 (21), p.568-5618 |
| issn | 2041-6520 2041-6539 |
| language | eng |
| recordid | cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_10231430 |
| source | PubMed Central |
| subjects | Alkynes Amides Boron Carbonates Catalysis Chemical synthesis Chemistry Esters Lewis acid Noble metals Reaction mechanisms Stereochemistry Stereoselectivity Substitutes |
| title | Atom-economic and stereoselective catalytic synthesis of fully substituted enol esters/carbonates of amides in acyclic systems enabled by boron Lewis acid catalysis |
| url | http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-09-22T01%3A30%3A50IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Atom-economic%20and%20stereoselective%20catalytic%20synthesis%20of%20fully%20substituted%20enol%20esters/carbonates%20of%20amides%20in%20acyclic%20systems%20enabled%20by%20boron%20Lewis%20acid%20catalysis&rft.jtitle=Chemical%20science%20(Cambridge)&rft.au=Xiao,%20Yuanjiu&rft.date=2023-05-31&rft.volume=14&rft.issue=21&rft.spage=568&rft.epage=5618&rft.pages=568-5618&rft.issn=2041-6520&rft.eissn=2041-6539&rft_id=info:doi/10.1039/d3sc01394d&rft_dat=%3Cproquest_pubme%3E2820965872%3C/proquest_pubme%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-c429t-42f47afba6c133de07bb818c758bb6e911df2145d3b1b60810d70acb5b73ddd03%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=2820965872&rft_id=info:pmid/37265723&rfr_iscdi=true |