Catalytic Regio‐ and Enantioselective Protonation for the Synthesis of Chiral Allenes: Synergistic Effect of the Counterion and Water

A highly enantioselective tandem Pudovik addition/[1,2]‐phospha‐Brook rearrangement of α‐alkynylketoamides with diarylphosphine oxides was achieved with a N,N′‐dioxide/ScIII complex as the catalyst. This protocol features broad substrate scope, high regio‐ and enantioselectivity, and good functional...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Angewandte Chemie 2022-07, Vol.134 (27), p.n/a
Hauptverfasser: Lin, Qianchi, Zheng, Sujuan, Chen, Long, Wu, Jin, Li, Jinzhao, Liu, Peizhi, Dong, Shunxi, Liu, Xiaohua, Peng, Qian, Feng, Xiaoming
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page n/a
container_issue 27
container_start_page
container_title Angewandte Chemie
container_volume 134
creator Lin, Qianchi
Zheng, Sujuan
Chen, Long
Wu, Jin
Li, Jinzhao
Liu, Peizhi
Dong, Shunxi
Liu, Xiaohua
Peng, Qian
Feng, Xiaoming
description A highly enantioselective tandem Pudovik addition/[1,2]‐phospha‐Brook rearrangement of α‐alkynylketoamides with diarylphosphine oxides was achieved with a N,N′‐dioxide/ScIII complex as the catalyst. This protocol features broad substrate scope, high regio‐ and enantioselectivity, and good functional‐group compatibility, providing a straightforward route to various trisubstituted allenes with a diarylphosphinate functionality in good yields with high enantioselectivities (up to 97 % yield, 96 % ee). Control experiments and theoretical calculations revealed that a synergistic effect of the counterion and water was critical for the regio‐ and enantioselective protonation after [1,2]‐phospha‐Brook rearrangement. The synthetic utility of this methodology was demonstrated by the conversion of products into complex bridged polycyclic architectures through intramolecular dearomatizing arene/allene cycloaddition. Pudovik addition/[1,2]‐phospha‐Brook rearrangement mediated by a chiral ScIII/N,N′‐dioxide complex led to axially chiral trisubstituted allenes with a diarylphosphinate moiety. A synergistic effect of the counterion and water enabled regio‐ and enantioselective protonation after [1,2]‐phospha‐Brook rearrangement. Intramolecular dearomatization of N‐Ph‐substituted products gave bridged polycyclic architectures through stereospecific Himbert reaction.
doi_str_mv 10.1002/ange.202203650
format Article
fullrecord <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_2681206141</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2681206141</sourcerecordid><originalsourceid>FETCH-LOGICAL-c1620-655db19d4a7a64949a3e226a43a104d317f70b83eaee95f5f72d3cea12000ea13</originalsourceid><addsrcrecordid>eNqFkD9PwzAQxS0EEqWwMltiTrEdJ2nYqqgUJASIP2KMjuRcjIINdgrKxsbKZ-STYKsIRqanO__eO_kRss_ZhDMmDsEscSKYECzNM7ZBRjwTPEmLrNgkI8akTKZClttkx_tHxlguinJEPirooRt63dArXGr79f5JwbR0bsD02nrssOn1K9JLZ3trIOwMVdbR_gHp9WCCeO2pVbR60A46Ous6NOiP4iO6pfYxeq5UiIlUtFV2ZXp0MSmeuoMw7JItBZ3HvR8dk9vj-U11kpxdLE6r2VnS8FywJM-y9p6XrYQCclnKElIUIgeZAmeyTXmhCnY_TREQy0xlqhBt2iBwEX4cJB2Tg3Xus7MvK_R9_WhXzoSTtcinAcu5jNRkTTXOeu9Q1c9OP4Ebas7qWHYdy65_yw6Gcm140x0O_9D17Hwx__N-A59HhZ0</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2681206141</pqid></control><display><type>article</type><title>Catalytic Regio‐ and Enantioselective Protonation for the Synthesis of Chiral Allenes: Synergistic Effect of the Counterion and Water</title><source>Access via Wiley Online Library</source><creator>Lin, Qianchi ; Zheng, Sujuan ; Chen, Long ; Wu, Jin ; Li, Jinzhao ; Liu, Peizhi ; Dong, Shunxi ; Liu, Xiaohua ; Peng, Qian ; Feng, Xiaoming</creator><creatorcontrib>Lin, Qianchi ; Zheng, Sujuan ; Chen, Long ; Wu, Jin ; Li, Jinzhao ; Liu, Peizhi ; Dong, Shunxi ; Liu, Xiaohua ; Peng, Qian ; Feng, Xiaoming</creatorcontrib><description>A highly enantioselective tandem Pudovik addition/[1,2]‐phospha‐Brook rearrangement of α‐alkynylketoamides with diarylphosphine oxides was achieved with a N,N′‐dioxide/ScIII complex as the catalyst. This protocol features broad substrate scope, high regio‐ and enantioselectivity, and good functional‐group compatibility, providing a straightforward route to various trisubstituted allenes with a diarylphosphinate functionality in good yields with high enantioselectivities (up to 97 % yield, 96 % ee). Control experiments and theoretical calculations revealed that a synergistic effect of the counterion and water was critical for the regio‐ and enantioselective protonation after [1,2]‐phospha‐Brook rearrangement. The synthetic utility of this methodology was demonstrated by the conversion of products into complex bridged polycyclic architectures through intramolecular dearomatizing arene/allene cycloaddition. Pudovik addition/[1,2]‐phospha‐Brook rearrangement mediated by a chiral ScIII/N,N′‐dioxide complex led to axially chiral trisubstituted allenes with a diarylphosphinate moiety. A synergistic effect of the counterion and water enabled regio‐ and enantioselective protonation after [1,2]‐phospha‐Brook rearrangement. Intramolecular dearomatization of N‐Ph‐substituted products gave bridged polycyclic architectures through stereospecific Himbert reaction.</description><identifier>ISSN: 0044-8249</identifier><identifier>EISSN: 1521-3757</identifier><identifier>DOI: 10.1002/ange.202203650</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Axial Chiral Allenes ; Catalysts ; Chemistry ; Cycloaddition ; Enantiomers ; Lewis Acid Catalysis ; Phospha-Brook Rearrangement ; Protonation ; Substrates ; Synergistic Effect ; Water</subject><ispartof>Angewandte Chemie, 2022-07, Vol.134 (27), p.n/a</ispartof><rights>2022 Wiley‐VCH GmbH</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1620-655db19d4a7a64949a3e226a43a104d317f70b83eaee95f5f72d3cea12000ea13</citedby><cites>FETCH-LOGICAL-c1620-655db19d4a7a64949a3e226a43a104d317f70b83eaee95f5f72d3cea12000ea13</cites><orcidid>0000-0001-7256-7653 ; 0000-0003-4507-0478 ; 0000-0001-9555-0555 ; 0000-0001-7670-693X ; 0000-0002-3018-3085 ; 0000-0002-9746-9563 ; 0000-0002-1218-5976 ; 0000-0003-2287-5417</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%2Fange.202203650$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fange.202203650$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids></links><search><creatorcontrib>Lin, Qianchi</creatorcontrib><creatorcontrib>Zheng, Sujuan</creatorcontrib><creatorcontrib>Chen, Long</creatorcontrib><creatorcontrib>Wu, Jin</creatorcontrib><creatorcontrib>Li, Jinzhao</creatorcontrib><creatorcontrib>Liu, Peizhi</creatorcontrib><creatorcontrib>Dong, Shunxi</creatorcontrib><creatorcontrib>Liu, Xiaohua</creatorcontrib><creatorcontrib>Peng, Qian</creatorcontrib><creatorcontrib>Feng, Xiaoming</creatorcontrib><title>Catalytic Regio‐ and Enantioselective Protonation for the Synthesis of Chiral Allenes: Synergistic Effect of the Counterion and Water</title><title>Angewandte Chemie</title><description>A highly enantioselective tandem Pudovik addition/[1,2]‐phospha‐Brook rearrangement of α‐alkynylketoamides with diarylphosphine oxides was achieved with a N,N′‐dioxide/ScIII complex as the catalyst. This protocol features broad substrate scope, high regio‐ and enantioselectivity, and good functional‐group compatibility, providing a straightforward route to various trisubstituted allenes with a diarylphosphinate functionality in good yields with high enantioselectivities (up to 97 % yield, 96 % ee). Control experiments and theoretical calculations revealed that a synergistic effect of the counterion and water was critical for the regio‐ and enantioselective protonation after [1,2]‐phospha‐Brook rearrangement. The synthetic utility of this methodology was demonstrated by the conversion of products into complex bridged polycyclic architectures through intramolecular dearomatizing arene/allene cycloaddition. Pudovik addition/[1,2]‐phospha‐Brook rearrangement mediated by a chiral ScIII/N,N′‐dioxide complex led to axially chiral trisubstituted allenes with a diarylphosphinate moiety. A synergistic effect of the counterion and water enabled regio‐ and enantioselective protonation after [1,2]‐phospha‐Brook rearrangement. Intramolecular dearomatization of N‐Ph‐substituted products gave bridged polycyclic architectures through stereospecific Himbert reaction.</description><subject>Axial Chiral Allenes</subject><subject>Catalysts</subject><subject>Chemistry</subject><subject>Cycloaddition</subject><subject>Enantiomers</subject><subject>Lewis Acid Catalysis</subject><subject>Phospha-Brook Rearrangement</subject><subject>Protonation</subject><subject>Substrates</subject><subject>Synergistic Effect</subject><subject>Water</subject><issn>0044-8249</issn><issn>1521-3757</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNqFkD9PwzAQxS0EEqWwMltiTrEdJ2nYqqgUJASIP2KMjuRcjIINdgrKxsbKZ-STYKsIRqanO__eO_kRss_ZhDMmDsEscSKYECzNM7ZBRjwTPEmLrNgkI8akTKZClttkx_tHxlguinJEPirooRt63dArXGr79f5JwbR0bsD02nrssOn1K9JLZ3trIOwMVdbR_gHp9WCCeO2pVbR60A46Ous6NOiP4iO6pfYxeq5UiIlUtFV2ZXp0MSmeuoMw7JItBZ3HvR8dk9vj-U11kpxdLE6r2VnS8FywJM-y9p6XrYQCclnKElIUIgeZAmeyTXmhCnY_TREQy0xlqhBt2iBwEX4cJB2Tg3Xus7MvK_R9_WhXzoSTtcinAcu5jNRkTTXOeu9Q1c9OP4Ebas7qWHYdy65_yw6Gcm140x0O_9D17Hwx__N-A59HhZ0</recordid><startdate>20220704</startdate><enddate>20220704</enddate><creator>Lin, Qianchi</creator><creator>Zheng, Sujuan</creator><creator>Chen, Long</creator><creator>Wu, Jin</creator><creator>Li, Jinzhao</creator><creator>Liu, Peizhi</creator><creator>Dong, Shunxi</creator><creator>Liu, Xiaohua</creator><creator>Peng, Qian</creator><creator>Feng, Xiaoming</creator><general>Wiley Subscription Services, Inc</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><orcidid>https://orcid.org/0000-0001-7256-7653</orcidid><orcidid>https://orcid.org/0000-0003-4507-0478</orcidid><orcidid>https://orcid.org/0000-0001-9555-0555</orcidid><orcidid>https://orcid.org/0000-0001-7670-693X</orcidid><orcidid>https://orcid.org/0000-0002-3018-3085</orcidid><orcidid>https://orcid.org/0000-0002-9746-9563</orcidid><orcidid>https://orcid.org/0000-0002-1218-5976</orcidid><orcidid>https://orcid.org/0000-0003-2287-5417</orcidid></search><sort><creationdate>20220704</creationdate><title>Catalytic Regio‐ and Enantioselective Protonation for the Synthesis of Chiral Allenes: Synergistic Effect of the Counterion and Water</title><author>Lin, Qianchi ; Zheng, Sujuan ; Chen, Long ; Wu, Jin ; Li, Jinzhao ; Liu, Peizhi ; Dong, Shunxi ; Liu, Xiaohua ; Peng, Qian ; Feng, Xiaoming</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c1620-655db19d4a7a64949a3e226a43a104d317f70b83eaee95f5f72d3cea12000ea13</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Axial Chiral Allenes</topic><topic>Catalysts</topic><topic>Chemistry</topic><topic>Cycloaddition</topic><topic>Enantiomers</topic><topic>Lewis Acid Catalysis</topic><topic>Phospha-Brook Rearrangement</topic><topic>Protonation</topic><topic>Substrates</topic><topic>Synergistic Effect</topic><topic>Water</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Lin, Qianchi</creatorcontrib><creatorcontrib>Zheng, Sujuan</creatorcontrib><creatorcontrib>Chen, Long</creatorcontrib><creatorcontrib>Wu, Jin</creatorcontrib><creatorcontrib>Li, Jinzhao</creatorcontrib><creatorcontrib>Liu, Peizhi</creatorcontrib><creatorcontrib>Dong, Shunxi</creatorcontrib><creatorcontrib>Liu, Xiaohua</creatorcontrib><creatorcontrib>Peng, Qian</creatorcontrib><creatorcontrib>Feng, Xiaoming</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Angewandte Chemie</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Lin, Qianchi</au><au>Zheng, Sujuan</au><au>Chen, Long</au><au>Wu, Jin</au><au>Li, Jinzhao</au><au>Liu, Peizhi</au><au>Dong, Shunxi</au><au>Liu, Xiaohua</au><au>Peng, Qian</au><au>Feng, Xiaoming</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Catalytic Regio‐ and Enantioselective Protonation for the Synthesis of Chiral Allenes: Synergistic Effect of the Counterion and Water</atitle><jtitle>Angewandte Chemie</jtitle><date>2022-07-04</date><risdate>2022</risdate><volume>134</volume><issue>27</issue><epage>n/a</epage><issn>0044-8249</issn><eissn>1521-3757</eissn><abstract>A highly enantioselective tandem Pudovik addition/[1,2]‐phospha‐Brook rearrangement of α‐alkynylketoamides with diarylphosphine oxides was achieved with a N,N′‐dioxide/ScIII complex as the catalyst. This protocol features broad substrate scope, high regio‐ and enantioselectivity, and good functional‐group compatibility, providing a straightforward route to various trisubstituted allenes with a diarylphosphinate functionality in good yields with high enantioselectivities (up to 97 % yield, 96 % ee). Control experiments and theoretical calculations revealed that a synergistic effect of the counterion and water was critical for the regio‐ and enantioselective protonation after [1,2]‐phospha‐Brook rearrangement. The synthetic utility of this methodology was demonstrated by the conversion of products into complex bridged polycyclic architectures through intramolecular dearomatizing arene/allene cycloaddition. Pudovik addition/[1,2]‐phospha‐Brook rearrangement mediated by a chiral ScIII/N,N′‐dioxide complex led to axially chiral trisubstituted allenes with a diarylphosphinate moiety. A synergistic effect of the counterion and water enabled regio‐ and enantioselective protonation after [1,2]‐phospha‐Brook rearrangement. Intramolecular dearomatization of N‐Ph‐substituted products gave bridged polycyclic architectures through stereospecific Himbert reaction.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/ange.202203650</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0001-7256-7653</orcidid><orcidid>https://orcid.org/0000-0003-4507-0478</orcidid><orcidid>https://orcid.org/0000-0001-9555-0555</orcidid><orcidid>https://orcid.org/0000-0001-7670-693X</orcidid><orcidid>https://orcid.org/0000-0002-3018-3085</orcidid><orcidid>https://orcid.org/0000-0002-9746-9563</orcidid><orcidid>https://orcid.org/0000-0002-1218-5976</orcidid><orcidid>https://orcid.org/0000-0003-2287-5417</orcidid></addata></record>
fulltext fulltext
identifier ISSN: 0044-8249
ispartof Angewandte Chemie, 2022-07, Vol.134 (27), p.n/a
issn 0044-8249
1521-3757
language eng
recordid cdi_proquest_journals_2681206141
source Access via Wiley Online Library
subjects Axial Chiral Allenes
Catalysts
Chemistry
Cycloaddition
Enantiomers
Lewis Acid Catalysis
Phospha-Brook Rearrangement
Protonation
Substrates
Synergistic Effect
Water
title Catalytic Regio‐ and Enantioselective Protonation for the Synthesis of Chiral Allenes: Synergistic Effect of the Counterion and Water
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-21T18%3A21%3A58IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Catalytic%20Regio%E2%80%90%20and%20Enantioselective%20Protonation%20for%20the%20Synthesis%20of%20Chiral%20Allenes:%20Synergistic%20Effect%20of%20the%20Counterion%20and%20Water&rft.jtitle=Angewandte%20Chemie&rft.au=Lin,%20Qianchi&rft.date=2022-07-04&rft.volume=134&rft.issue=27&rft.epage=n/a&rft.issn=0044-8249&rft.eissn=1521-3757&rft_id=info:doi/10.1002/ange.202203650&rft_dat=%3Cproquest_cross%3E2681206141%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2681206141&rft_id=info:pmid/&rfr_iscdi=true