An Organocopper(III) Fluoride Triggering C-CF 3 Bond Formation

Copper(III) fluorides are catalytically competent, yet elusive, intermediates in cross-coupling. The synthesis of [PPh ][Cu (CF ) F] (2), the first stable (isolable) Cu -F, was accomplished via chloride addition to [Cu (CF ) (py)] (1) yielding [PPh ][Cu (CF ) Cl(py)] (1⋅Cl), followed by treatment wi...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2024-03, Vol.63 (11), p.e202319412
Main Authors: Joven-Sancho, Daniel, Echeverri, Andrea, Saffon-Merceron, Nathalie, Contreras-García, Julia, Nebra, Noel
Format: Article
Language:English
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-c1076-3c47314d0ccf5d36cbc5b35c72977f86e497acc37afc5c11b6566a5fb313910c3
cites cdi_FETCH-LOGICAL-c1076-3c47314d0ccf5d36cbc5b35c72977f86e497acc37afc5c11b6566a5fb313910c3
container_end_page
container_issue 11
container_start_page e202319412
container_title Angewandte Chemie International Edition
container_volume 63
creator Joven-Sancho, Daniel
Echeverri, Andrea
Saffon-Merceron, Nathalie
Contreras-García, Julia
Nebra, Noel
description Copper(III) fluorides are catalytically competent, yet elusive, intermediates in cross-coupling. The synthesis of [PPh ][Cu (CF ) F] (2), the first stable (isolable) Cu -F, was accomplished via chloride addition to [Cu (CF ) (py)] (1) yielding [PPh ][Cu (CF ) Cl(py)] (1⋅Cl), followed by treatment with AgF. The Cu halides 1⋅Cl and 2 were fully characterized using nuclear magnetic resonance (NMR) spectroscopy, single crystal X-ray diffraction (Sc-XRD) and elemental analysis (EA). Complex 2 proved capable of forging C-CF bonds from silyl-capped alkynes. In-depth mechanistic studies combining probes, theoretical calculations, trapping of intermediate 4 ([PPh ][Cu (CF ) (C≡CPh)]) and radical tests unveil the key role of the Cu acetylides that undergo facile 2e reductive elimination furnishing the trifluoromethylated alkynes (RC≡CCF ), which are industrially relevant synthons in drug discovery, pharma and agrochemistry.
doi_str_mv 10.1002/anie.202319412
format article
fullrecord <record><control><sourceid>pubmed_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1002_anie_202319412</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>38147576</sourcerecordid><originalsourceid>FETCH-LOGICAL-c1076-3c47314d0ccf5d36cbc5b35c72977f86e497acc37afc5c11b6566a5fb313910c3</originalsourceid><addsrcrecordid>eNo9kDFPwzAUhC0EoqWwMiKPMCT45cV2siCViECkSl3KHDkvThTUxJFDB_49qQqd7oa7k-5j7B5ECEJEz2bobBiJCCGNIbpgS5ARBKg1Xs4-Rgx0ImHBbqbpa84niVDXbIEJxFpqtWQv64FvfWsGR24crX8siuKJ5_uD811t-c53bWt9N7Q8C7KcI391Q81z53vz3bnhll01Zj_Zuz9dsc_8bZd9BJvte5GtNwGB0CpAijVCXAuiRtaoqCJZoSQdpVo3ibJxqg0RatOQJIBKSaWMbCoETEEQrlh42iXvpsnbphx91xv_U4IojyDKI4jyDGIuPJwK46HqbX2O_z_HX-FRVz8</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>An Organocopper(III) Fluoride Triggering C-CF 3 Bond Formation</title><source>Wiley</source><creator>Joven-Sancho, Daniel ; Echeverri, Andrea ; Saffon-Merceron, Nathalie ; Contreras-García, Julia ; Nebra, Noel</creator><creatorcontrib>Joven-Sancho, Daniel ; Echeverri, Andrea ; Saffon-Merceron, Nathalie ; Contreras-García, Julia ; Nebra, Noel</creatorcontrib><description>Copper(III) fluorides are catalytically competent, yet elusive, intermediates in cross-coupling. The synthesis of [PPh ][Cu (CF ) F] (2), the first stable (isolable) Cu -F, was accomplished via chloride addition to [Cu (CF ) (py)] (1) yielding [PPh ][Cu (CF ) Cl(py)] (1⋅Cl), followed by treatment with AgF. The Cu halides 1⋅Cl and 2 were fully characterized using nuclear magnetic resonance (NMR) spectroscopy, single crystal X-ray diffraction (Sc-XRD) and elemental analysis (EA). Complex 2 proved capable of forging C-CF bonds from silyl-capped alkynes. In-depth mechanistic studies combining probes, theoretical calculations, trapping of intermediate 4 ([PPh ][Cu (CF ) (C≡CPh)]) and radical tests unveil the key role of the Cu acetylides that undergo facile 2e reductive elimination furnishing the trifluoromethylated alkynes (RC≡CCF ), which are industrially relevant synthons in drug discovery, pharma and agrochemistry.</description><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202319412</identifier><identifier>PMID: 38147576</identifier><language>eng</language><publisher>Germany</publisher><ispartof>Angewandte Chemie International Edition, 2024-03, Vol.63 (11), p.e202319412</ispartof><rights>2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1076-3c47314d0ccf5d36cbc5b35c72977f86e497acc37afc5c11b6566a5fb313910c3</citedby><cites>FETCH-LOGICAL-c1076-3c47314d0ccf5d36cbc5b35c72977f86e497acc37afc5c11b6566a5fb313910c3</cites><orcidid>0000-0002-4209-9235 ; 0000-0002-8947-9526 ; 0000-0002-0301-4163 ; 0000-0002-0204-7713 ; 0000-0002-4605-2741</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,786,790,27957,27958</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/38147576$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Joven-Sancho, Daniel</creatorcontrib><creatorcontrib>Echeverri, Andrea</creatorcontrib><creatorcontrib>Saffon-Merceron, Nathalie</creatorcontrib><creatorcontrib>Contreras-García, Julia</creatorcontrib><creatorcontrib>Nebra, Noel</creatorcontrib><title>An Organocopper(III) Fluoride Triggering C-CF 3 Bond Formation</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>Copper(III) fluorides are catalytically competent, yet elusive, intermediates in cross-coupling. The synthesis of [PPh ][Cu (CF ) F] (2), the first stable (isolable) Cu -F, was accomplished via chloride addition to [Cu (CF ) (py)] (1) yielding [PPh ][Cu (CF ) Cl(py)] (1⋅Cl), followed by treatment with AgF. The Cu halides 1⋅Cl and 2 were fully characterized using nuclear magnetic resonance (NMR) spectroscopy, single crystal X-ray diffraction (Sc-XRD) and elemental analysis (EA). Complex 2 proved capable of forging C-CF bonds from silyl-capped alkynes. In-depth mechanistic studies combining probes, theoretical calculations, trapping of intermediate 4 ([PPh ][Cu (CF ) (C≡CPh)]) and radical tests unveil the key role of the Cu acetylides that undergo facile 2e reductive elimination furnishing the trifluoromethylated alkynes (RC≡CCF ), which are industrially relevant synthons in drug discovery, pharma and agrochemistry.</description><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNo9kDFPwzAUhC0EoqWwMiKPMCT45cV2siCViECkSl3KHDkvThTUxJFDB_49qQqd7oa7k-5j7B5ECEJEz2bobBiJCCGNIbpgS5ARBKg1Xs4-Rgx0ImHBbqbpa84niVDXbIEJxFpqtWQv64FvfWsGR24crX8siuKJ5_uD811t-c53bWt9N7Q8C7KcI391Q81z53vz3bnhll01Zj_Zuz9dsc_8bZd9BJvte5GtNwGB0CpAijVCXAuiRtaoqCJZoSQdpVo3ibJxqg0RatOQJIBKSaWMbCoETEEQrlh42iXvpsnbphx91xv_U4IojyDKI4jyDGIuPJwK46HqbX2O_z_HX-FRVz8</recordid><startdate>20240311</startdate><enddate>20240311</enddate><creator>Joven-Sancho, Daniel</creator><creator>Echeverri, Andrea</creator><creator>Saffon-Merceron, Nathalie</creator><creator>Contreras-García, Julia</creator><creator>Nebra, Noel</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0002-4209-9235</orcidid><orcidid>https://orcid.org/0000-0002-8947-9526</orcidid><orcidid>https://orcid.org/0000-0002-0301-4163</orcidid><orcidid>https://orcid.org/0000-0002-0204-7713</orcidid><orcidid>https://orcid.org/0000-0002-4605-2741</orcidid></search><sort><creationdate>20240311</creationdate><title>An Organocopper(III) Fluoride Triggering C-CF 3 Bond Formation</title><author>Joven-Sancho, Daniel ; Echeverri, Andrea ; Saffon-Merceron, Nathalie ; Contreras-García, Julia ; Nebra, Noel</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c1076-3c47314d0ccf5d36cbc5b35c72977f86e497acc37afc5c11b6566a5fb313910c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Joven-Sancho, Daniel</creatorcontrib><creatorcontrib>Echeverri, Andrea</creatorcontrib><creatorcontrib>Saffon-Merceron, Nathalie</creatorcontrib><creatorcontrib>Contreras-García, Julia</creatorcontrib><creatorcontrib>Nebra, Noel</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Joven-Sancho, Daniel</au><au>Echeverri, Andrea</au><au>Saffon-Merceron, Nathalie</au><au>Contreras-García, Julia</au><au>Nebra, Noel</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>An Organocopper(III) Fluoride Triggering C-CF 3 Bond Formation</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2024-03-11</date><risdate>2024</risdate><volume>63</volume><issue>11</issue><spage>e202319412</spage><pages>e202319412-</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Copper(III) fluorides are catalytically competent, yet elusive, intermediates in cross-coupling. The synthesis of [PPh ][Cu (CF ) F] (2), the first stable (isolable) Cu -F, was accomplished via chloride addition to [Cu (CF ) (py)] (1) yielding [PPh ][Cu (CF ) Cl(py)] (1⋅Cl), followed by treatment with AgF. The Cu halides 1⋅Cl and 2 were fully characterized using nuclear magnetic resonance (NMR) spectroscopy, single crystal X-ray diffraction (Sc-XRD) and elemental analysis (EA). Complex 2 proved capable of forging C-CF bonds from silyl-capped alkynes. In-depth mechanistic studies combining probes, theoretical calculations, trapping of intermediate 4 ([PPh ][Cu (CF ) (C≡CPh)]) and radical tests unveil the key role of the Cu acetylides that undergo facile 2e reductive elimination furnishing the trifluoromethylated alkynes (RC≡CCF ), which are industrially relevant synthons in drug discovery, pharma and agrochemistry.</abstract><cop>Germany</cop><pmid>38147576</pmid><doi>10.1002/anie.202319412</doi><orcidid>https://orcid.org/0000-0002-4209-9235</orcidid><orcidid>https://orcid.org/0000-0002-8947-9526</orcidid><orcidid>https://orcid.org/0000-0002-0301-4163</orcidid><orcidid>https://orcid.org/0000-0002-0204-7713</orcidid><orcidid>https://orcid.org/0000-0002-4605-2741</orcidid></addata></record>
fulltext fulltext
identifier ISSN: 1433-7851
ispartof Angewandte Chemie International Edition, 2024-03, Vol.63 (11), p.e202319412
issn 1433-7851
1521-3773
language eng
recordid cdi_crossref_primary_10_1002_anie_202319412
source Wiley
title An Organocopper(III) Fluoride Triggering C-CF 3 Bond Formation
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-09-23T06%3A31%3A43IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-pubmed_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=An%20Organocopper(III)%20Fluoride%20Triggering%20C-CF%203%20Bond%20Formation&rft.jtitle=Angewandte%20Chemie%20International%20Edition&rft.au=Joven-Sancho,%20Daniel&rft.date=2024-03-11&rft.volume=63&rft.issue=11&rft.spage=e202319412&rft.pages=e202319412-&rft.issn=1433-7851&rft.eissn=1521-3773&rft_id=info:doi/10.1002/anie.202319412&rft_dat=%3Cpubmed_cross%3E38147576%3C/pubmed_cross%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-c1076-3c47314d0ccf5d36cbc5b35c72977f86e497acc37afc5c11b6566a5fb313910c3%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_id=info:pmid/38147576&rfr_iscdi=true