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...

Full description

Saved in:
Bibliographic Details
Published inChemistry letters Vol. 51; no. 10; pp. 985 - 988
Main Authors Hirasawa, Shun, Kurashima, Takashi, Hasegawa, Takahiro, Souma, Kazunori, Kanomata, Nobuhiro
Format Journal Article
LanguageEnglish
Published TOKYO Chemical Soc Japan 05.10.2022
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
Azaspirene
Crystallization-induced diastereomer transformation
(-)-AZASPIRENE
ASYMMETRIC TOTAL-SYNTHESIS
Angiogenic inhibitor
Online AccessGet more information

Cover

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