Total Synthesis of (+/-)-Azaspirene via Crystallization-induced Diastereomer Transformation
The total synthesis of racemic azaspirene was accomplished over 12 steps in a 17% overall yield via a convergent strategy featuring the coupling of isocyanate and 3(2H)-furanone and an intramolecular aldol reaction to construct the spiro core. Later, a complete conversion was achieved via the crysta...
Saved in:
Published in | Chemistry letters Vol. 51; no. 10; pp. 985 - 988 |
---|---|
Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
TOKYO
Chemical Soc Japan
05.10.2022
|
Subjects | |
Online Access | Get more information |
Cover
Loading…
Abstract | The total synthesis of racemic azaspirene was accomplished over 12 steps in a 17% overall yield via a convergent strategy featuring the coupling of isocyanate and 3(2H)-furanone and an intramolecular aldol reaction to construct the spiro core. Later, a complete conversion was achieved via the crystallization-induced diastereomer transformation of the kinetically favored epimer-produced primarily via spirocyclic construction-to the thermodynamically stable and desirable epimer. Finally, a stereo selective hydration produced the target azaspirene. |
---|---|
AbstractList | The total synthesis of racemic azaspirene was accomplished over 12 steps in a 17% overall yield via a convergent strategy featuring the coupling of isocyanate and 3(2H)-furanone and an intramolecular aldol reaction to construct the spiro core. Later, a complete conversion was achieved via the crystallization-induced diastereomer transformation of the kinetically favored epimer-produced primarily via spirocyclic construction-to the thermodynamically stable and desirable epimer. Finally, a stereo selective hydration produced the target azaspirene. |
Author | Hasegawa, Takahiro Kanomata, Nobuhiro Souma, Kazunori Kurashima, Takashi Hirasawa, Shun |
Author_xml | – sequence: 1 givenname: Shun surname: Hirasawa fullname: Hirasawa, Shun organization: Waseda Univ, Dept Chem & Biochem, Shinjuku Ku, Tokyo 1698555, Japan – sequence: 2 givenname: Takashi surname: Kurashima fullname: Kurashima, Takashi organization: Waseda Univ, Dept Chem & Biochem, Shinjuku Ku, Tokyo 1698555, Japan – sequence: 3 givenname: Takahiro surname: Hasegawa fullname: Hasegawa, Takahiro organization: Waseda Univ, Dept Chem & Biochem, Shinjuku Ku, Tokyo 1698555, Japan – sequence: 4 givenname: Kazunori surname: Souma fullname: Souma, Kazunori organization: Meiji Univ, Dept Appl Chem, Kawasaki, Kanagawa 2148571, Japan – sequence: 5 givenname: Nobuhiro surname: Kanomata fullname: Kanomata, Nobuhiro email: kanomata@waseda.jp organization: Waseda Univ, Dept Chem & Biochem, Shinjuku Ku, Tokyo 1698555, Japan |
BookMark | eNqNj01PAjEYhBujiYAe_Ad71JDC2y-2PZL1MyHxIJ48kG73baxZWrJdNPDrRfQHeJo5zDOZGZLTmCIScsVgwricTV074Ry4MSdkwITUFEqmTskAxGxGS-D8nAxz_gAAbQQfkLdl6m1bvOxi_4455CL54no8pTd0vrd5EzqMWHwGW1TdLh-SbdjbPqRIQ2y2DpviNtjcY4dpjV2x7GzMPnXrY-aCnHnbZrz80xF5vb9bVo908fzwVM0X1EklemqZNKi0Bl6qBg3MPDSlczUwwRTyRisE40xTgq9ByFoDq43nDoxntQLJR0T_9n5hnXx2AaPD1aYLa9vtVj9XlZZCioMDUYX-OK5K29gf0PH_Uf4NVyVqLA |
CitedBy_id | crossref_primary_10_1021_acs_joc_4c00090 |
Cites_doi | 10.1021/ol020104+ 10.3987/REV-20-944 10.1002/ejoc.201600766 10.1021/acs.joc.7b01224 10.1039/c8cc02315h 10.1039/c4ra09047k 10.1021/ol0506258 10.1246/bcsj.77.1703 10.1021/cr0406864 10.1016/j.tetlet.2008.11.021 10.1021/jo050664x 10.1002/adsc.202100473 10.1021/acs.joc.8b02223 10.1021/ja0276826 |
ContentType | Journal Article |
DBID | 1KM AHQBO BLEPL DTL |
DOI | 10.1246/cl.220299 |
DatabaseName | Index Chemicus Web of Science - Science Citation Index Expanded - 2022 Web of Science Core Collection Science Citation Index Expanded |
DatabaseTitle | Web of Science |
DatabaseTitleList | Web of Science |
Database_xml | – sequence: 1 dbid: 1KM name: Index Chemicus url: https://proxy.k.utb.cz/login?url=https://www.webofscience.com/wos/woscc/search-with-editions?editions=WOS.IC sourceTypes: Enrichment Source Index Database |
DeliveryMethod | no_fulltext_linktorsrc |
Discipline | Chemistry |
EISSN | 1348-0715 |
EndPage | 988 |
ExternalDocumentID | 000858434300003 |
FullText_t_NoSnippeting | true |
GroupedDBID | -~X 0R~ 1KM 29B 53G 5GY 6J9 AAPXW AAUAY ABCQX ABEFU ABXVV ABZEH ACGFO ACIWK ACNCT ADIPN AENEX ALMA_UNASSIGNED_HOLDINGS BCRHZ BLEPL CS3 DTL DU5 EBS EJD GROUPED_WOS_SCIENCE_CITATION_INDEX_EXPANDED JSF JSI KOP L7B OJZSN OK1 OWPYF OXVGQ P2P RAD RJT ROX SJN TWZ UPT ~02 |
ID | FETCH-LOGICAL-c453t-a149e5880275de906f0d7ccb01315e2d85e09c9d70fb034b801b9f2c09f1b5042 |
ISICitedReferencesCount | 1 |
ISICitedReferencesURI | https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=Summon&SrcAuth=ProQuest&DestApp=WOS&DestLinkType=CitingArticles&UT=000858434300003 |
ISSN | 0366-7022 |
IngestDate | Fri Oct 18 20:02:33 EDT 2024 Wed Sep 18 10:07:21 EDT 2024 |
IsDoiOpenAccess | false |
IsOpenAccess | true |
IsPeerReviewed | true |
IsScholarly | true |
Issue | 10 |
Keywords | Azaspirene Crystallization-induced diastereomer transformation (-)-AZASPIRENE ASYMMETRIC TOTAL-SYNTHESIS Angiogenic inhibitor |
Language | English |
LinkModel | OpenURL |
LogoURL | https://exlibris-pub.s3.amazonaws.com/fromwos-v2.jpg |
MergedId | FETCHMERGED-LOGICAL-c453t-a149e5880275de906f0d7ccb01315e2d85e09c9d70fb034b801b9f2c09f1b5042 |
OpenAccessLink | http://dx.doi.org/10.1246/cl.220299 |
PageCount | 4 |
ParticipantIDs | webofscience_primary_000858434300003CitationCount webofscience_primary_000858434300003 |
PublicationCentury | 2000 |
PublicationDate | 2022-10-05 |
PublicationDateYYYYMMDD | 2022-10-05 |
PublicationDate_xml | – month: 10 year: 2022 text: 2022-10-05 day: 05 |
PublicationDecade | 2020 |
PublicationPlace | TOKYO |
PublicationPlace_xml | – name: TOKYO |
PublicationTitle | Chemistry letters |
PublicationTitleAbbrev | CHEM LETT |
PublicationYear | 2022 |
Publisher | Chemical Soc Japan |
Publisher_xml | – name: Chemical Soc Japan |
References | NICOLAOU, KC (WOS:A1995QC77600007) 1995; 117 Sugi, M (WOS:000386920100013) 2016; 2016 Tanaka, K (WOS:000719566900001) 2021; 102 Aoki, SY (WOS:000224402000012) 2004; 77 Kanomata, N (WOS:000166894400020) 2001; 42 Kang, T (WOS:000411304500009) 2017; 82 Brands, KMJ (WOS:000238973000006) 2006; 106 Aoki, S (WOS:000188256600009) 2004; 62 Kolarovic, A (WOS:000661319500001) 2021; 363 Jo, D (WOS:000436029000021) 2018; 54 Hirasawa, S (WOS:000452929900021) 2018; 83 Hayashi, Y (WOS:000178514700010) 2002; 124 Kanomata, N (WOS:000263253500009) 2009; 50 Emoto, M (WOS:000354267200034) 2015; 35 Ueda, T (WOS:000229574300019) 2005; 7 Mo, XH (WOS:000344325400036) 2014; 4 Legault, C. Y (000858434300003.14) 2009 Hayashi, Y (WOS:000230355200036) 2005; 70 Asami, Y (WOS:000177617000010) 2002; 4 |
References_xml | – volume: 4 start-page: 2845 year: 2002 ident: WOS:000177617000010 article-title: Azaspirene: A novel angiogenesis inhibitor containing a 1-oxa-7-azaspiro[4.4]non-2-ene-4,6-dione skeleton produced by the fungus Neosartotya sp. publication-title: ORGANIC LETTERS doi: 10.1021/ol020104+ contributor: fullname: Asami, Y – volume: 102 start-page: 1235 year: 2021 ident: WOS:000719566900001 article-title: HIGHLY OXIDIZED gamma-LACTAM-CONTAINING NATURAL PRODUCTS: TOTAL SYNTHESIS AND BIOLOGICAL EVALUATION publication-title: HETEROCYCLES doi: 10.3987/REV-20-944 contributor: fullname: Tanaka, K – volume: 2016 start-page: 4834 year: 2016 ident: WOS:000386920100013 article-title: Asymmetric Total Synthesis of (-)-Azaspirene by Utilizing Ti-Claisen Condensation and Ti-Direct Aldol Reaction publication-title: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY doi: 10.1002/ejoc.201600766 contributor: fullname: Sugi, M – volume: 82 start-page: 9335 year: 2017 ident: WOS:000411304500009 article-title: Six-Step Total Synthesis of Azaspirene publication-title: JOURNAL OF ORGANIC CHEMISTRY doi: 10.1021/acs.joc.7b01224 contributor: fullname: Kang, T – volume: 54 start-page: 6750 year: 2018 ident: WOS:000436029000021 article-title: Total syntheses of spirocyclic PKS-NRPS-based fungal metabolites publication-title: CHEMICAL COMMUNICATIONS doi: 10.1039/c8cc02315h contributor: fullname: Jo, D – volume: 4 start-page: 50566 year: 2014 ident: WOS:000344325400036 article-title: Naturally occurring tetramic acid products: isolation, structure elucidation and biological activity publication-title: RSC ADVANCES doi: 10.1039/c4ra09047k contributor: fullname: Mo, XH – volume: 7 start-page: 2365 year: 2005 ident: WOS:000229574300019 article-title: Synthesis of planar-chiral paracyclophanes via samarium(II)-catalyzed intramolecular pinacol coupling publication-title: ORGANIC LETTERS doi: 10.1021/ol0506258 contributor: fullname: Ueda, T – volume: 77 start-page: 1703 year: 2004 ident: WOS:000224402000012 article-title: Total syntheses of natural pseurotins A, F-2, and azaspirene publication-title: BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN doi: 10.1246/bcsj.77.1703 contributor: fullname: Aoki, SY – volume: 106 start-page: 2711 year: 2006 ident: WOS:000238973000006 article-title: Crystallization-induced diastereomer transformations publication-title: CHEMICAL REVIEWS doi: 10.1021/cr0406864 contributor: fullname: Brands, KMJ – volume: 42 start-page: 1045 year: 2001 ident: WOS:000166894400020 article-title: Stereocontrol of molecular jump-rope: crystallization-induced asymmetric transformation of planar-chiral cyclophanes publication-title: TETRAHEDRON LETTERS contributor: fullname: Kanomata, N – volume: 50 start-page: 409 year: 2009 ident: WOS:000263253500009 article-title: Synchronized stereocontrol of planar chirality by crystallization-induced asymmetric transformation publication-title: TETRAHEDRON LETTERS doi: 10.1016/j.tetlet.2008.11.021 contributor: fullname: Kanomata, N – volume: 35 start-page: 2739 year: 2015 ident: WOS:000354267200034 article-title: Azaspirene Analogs Inhibit the Growth of Human Uterine Carcinosarcoma In Vitro and In Vivo publication-title: ANTICANCER RESEARCH contributor: fullname: Emoto, M – volume: 70 start-page: 5643 year: 2005 ident: WOS:000230355200036 article-title: First asymmetric total synthesis of synerazol, an antifungal antibiotic, and determination of its absolute stereochemistry publication-title: JOURNAL OF ORGANIC CHEMISTRY doi: 10.1021/jo050664x contributor: fullname: Hayashi, Y – volume: 363 start-page: 4110 year: 2021 ident: WOS:000661319500001 article-title: State of the Art in Crystallization-Induced Diastereomer Transformations publication-title: ADVANCED SYNTHESIS & CATALYSIS doi: 10.1002/adsc.202100473 contributor: fullname: Kolarovic, A – volume: 117 start-page: 634 year: 1995 ident: WOS:A1995QC77600007 article-title: TOTAL SYNTHESIS OF TAXOL .2. CONSTRUCTION OF A-RING AND C-RING INTERMEDIATES AND INITIAL ATTEMPTS TO CONSTRUCT THE ABC RING-SYSTEM publication-title: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY contributor: fullname: NICOLAOU, KC – volume: 62 start-page: 161 year: 2004 ident: WOS:000188256600009 article-title: Total syntheses of natural pseurotins a and F-2 and azaspirene publication-title: HETEROCYCLES contributor: fullname: Aoki, S – volume: 83 start-page: 14457 year: 2018 ident: WOS:000452929900021 article-title: Elucidation of Racemization Process of Azaspirene Skeleton in Neutral Aqueous Media publication-title: JOURNAL OF ORGANIC CHEMISTRY doi: 10.1021/acs.joc.8b02223 contributor: fullname: Hirasawa, S – volume: 124 start-page: 12078 year: 2002 ident: WOS:000178514700010 article-title: Asymmetric total synthesis of (-)-azaspirene, a novel angiogenesis inhibitor publication-title: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY doi: 10.1021/ja0276826 contributor: fullname: Hayashi, Y – year: 2009 ident: 000858434300003.14 publication-title: Ray-tracing rendering by using CYLview, 1.0b contributor: fullname: Legault, C. Y |
SSID | ssj0008932 |
Score | 2.419865 |
Snippet | The total synthesis of racemic azaspirene was accomplished over 12 steps in a 17% overall yield via a convergent strategy featuring the coupling of isocyanate... |
Source | Web of Science |
SourceID | webofscience |
SourceType | Enrichment Source Index Database |
StartPage | 985 |
SubjectTerms | Chemistry Chemistry, Multidisciplinary Physical Sciences Science & Technology |
Title | Total Synthesis of (+/-)-Azaspirene via Crystallization-induced Diastereomer Transformation |
URI | http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=Summon&SrcAuth=ProQuest&DestApp=WOS&DestLinkType=FullRecord&UT=000858434300003 |
Volume | 51 |
WOS | 000858434300003 |
WOSCitedRecordID | wos000858434300003 |
hasFullText | |
inHoldings | 1 |
isFullTextHit | |
isPrint | |
link | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwnV1Lb9NAEF6lcIAL4inKS3soEshy6tfa3mMJoKioXJJKlThU3vVsa5HYyI1Bzc_hlzK7XjZuKVLgYiV2snY8X2a-2fV8Q8ieSqUqAZC5BXnhJxwTlFyWgV9mksdQQCbM1MXR53R6nByesJPR6OfgqaVuJcZyfWNdyf9YFfehXXWV7D9Y1g2KO_A12he3aGHcbmfjRpcyzi5rZHFWWAQJ4-voHQ7pY47vH6wLvZKO_sz7XhXepL1EMrhY2NpLH_PxTq__v68KrZcAzRLaXu7c1TQOyevkd3M4b2GKgBwdn1ZtcVH8MDx0dt5tFva7VvdqWpoD8-KrfrNxeRdwZr-jD51XbeOme5puaUvV1l3dtNVwbgLTWrOy7tDkNA9mjfQOMfjXA-8WpykCpC9KHkPvfeMk1xVVbOierR6thWEwcLa8b_Zj4zbv2wP-ERIio4UsF-MIr7BvxnRVdvtaOHQPKRo6muvKWx3U4x2yk-Xah4afjlysR7bXr1PZH2O1q_Cc--6MN1IaQ1_m98k9m3fQgx5ED8gI6ofkjrPoI_LFgIk6MNFG0Tfevv92ACKKIKJ_AREdgoheBdFjcvzxw3wy9W3nDV8mLF75BebNwNC1RxkrgQepCvDPK_WcecggKnMGAZe8zAIlgjgRSHMEV5EMuAoFwzjwhNyqmxqeEirxJsSQsTTjIgkhFoyXnEVQSgVhKJJdsje8O6ffepGV02t3f5eE23xsYoXttaDD6tl2Qz8ndzfYfUFuK_QO8BKp5kq8Mtb-BXKdgNw |
link.rule.ids | 786 |
linkProvider | Clarivate |
openUrl | ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Total+Synthesis+of+%28%2B%2F-%29-Azaspirene+via+Crystallization-induced+Diastereomer+Transformation&rft.jtitle=Chemistry+letters&rft.au=Hirasawa%2C+Shun&rft.au=Kurashima%2C+Takashi&rft.au=Hasegawa%2C+Takahiro&rft.au=Souma%2C+Kazunori&rft.date=2022-10-05&rft.pub=Chemical+Soc+Japan&rft.issn=0366-7022&rft.eissn=1348-0715&rft.volume=51&rft.issue=10&rft.spage=985&rft.epage=988&rft_id=info:doi/10.1246%2Fcl.220299&rft.externalDBID=n%2Fa&rft.externalDocID=000858434300003 |
thumbnail_l | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/lc.gif&issn=0366-7022&client=summon |
thumbnail_m | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/mc.gif&issn=0366-7022&client=summon |
thumbnail_s | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/sc.gif&issn=0366-7022&client=summon |