Highly Site Selective Formal [5+2] and [4+2] Annulations of Isoxazoles with Heterosubstituted Alkynes by Platinum Catalysis: Rapid Access to Functionalized 1,3‐Oxazepines and 2,5‐Dihydropyridines

Platinum‐catalyzed formal [5+2] and [4+2] annulations of isoxazoles with heterosubstituted alkynes enabled the atom‐economical synthesis of valuable 1,3‐oxazepines and 2,5‐dihydropyridines, respectively. Importantly, this Pt catalysis not only led to unique reactivity dramatically divergent from tha...

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Published inAngewandte Chemie International Edition Vol. 56; no. 2; pp. 605 - 609
Main Authors Shen, Wen‐Bo, Xiao, Xin‐Yu, Sun, Qing, Zhou, Bo, Zhu, Xin‐Qi, Yan, Juan‐Zhu, Lu, Xin, Ye, Long‐Wu
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 09.01.2017
Wiley Subscription Services, Inc
EditionInternational ed. in English
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Abstract Platinum‐catalyzed formal [5+2] and [4+2] annulations of isoxazoles with heterosubstituted alkynes enabled the atom‐economical synthesis of valuable 1,3‐oxazepines and 2,5‐dihydropyridines, respectively. Importantly, this Pt catalysis not only led to unique reactivity dramatically divergent from that observed under Au catalysis, but also proceeded via unprecedented α‐imino platinum carbene intermediates. Gold's deviant relative: Platinum‐catalyzed formal [5+2] and [4+2] annulations of isoxazoles and heterosubstituted alkynes provided valuable 1,3‐oxazepines and 2,5‐dihydropyridines (see scheme). This reactivity deviates dramatically from that observed under gold catalysis and involves the generation of an α‐imino platinum carbene. A computational study provided evidence for the proposed mechanism of this unusual tandem sequence.
AbstractList Platinum‐catalyzed formal [5+2] and [4+2] annulations of isoxazoles with heterosubstituted alkynes enabled the atom‐economical synthesis of valuable 1,3‐oxazepines and 2,5‐dihydropyridines, respectively. Importantly, this Pt catalysis not only led to unique reactivity dramatically divergent from that observed under Au catalysis, but also proceeded via unprecedented α‐imino platinum carbene intermediates. Gold's deviant relative: Platinum‐catalyzed formal [5+2] and [4+2] annulations of isoxazoles and heterosubstituted alkynes provided valuable 1,3‐oxazepines and 2,5‐dihydropyridines (see scheme). This reactivity deviates dramatically from that observed under gold catalysis and involves the generation of an α‐imino platinum carbene. A computational study provided evidence for the proposed mechanism of this unusual tandem sequence.
Platinum-catalyzed formal [5+2] and [4+2] annulations of isoxazoles with heterosubstituted alkynes enabled the atom-economical synthesis of valuable 1,3-oxazepines and 2,5-dihydropyridines, respectively. Importantly, this Pt catalysis not only led to unique reactivity dramatically divergent from that observed under Au catalysis, but also proceeded via unprecedented [alpha]-imino platinum carbene intermediates.
Platinum-catalyzed formal [5+2] and [4+2] annulations of isoxazoles with heterosubstituted alkynes enabled the atom-economical synthesis of valuable 1,3-oxazepines and 2,5-dihydropyridines, respectively. Importantly, this Pt catalysis not only led to unique reactivity dramatically divergent from that observed under Au catalysis, but also proceeded via unprecedented α-imino platinum carbene intermediates.
Platinum-catalyzed formal [5+2] and [4+2] annulations of isoxazoles with heterosubstituted alkynes enabled the atom-economical synthesis of valuable 1,3-oxazepines and 2,5-dihydropyridines, respectively. Importantly, this Pt catalysis not only led to unique reactivity dramatically divergent from that observed under Au catalysis, but also proceeded via unprecedented a-imino platinum carbene intermediates.
Author Shen, Wen‐Bo
Sun, Qing
Zhou, Bo
Xiao, Xin‐Yu
Lu, Xin
Zhu, Xin‐Qi
Yan, Juan‐Zhu
Ye, Long‐Wu
Author_xml – sequence: 1
  givenname: Wen‐Bo
  surname: Shen
  fullname: Shen, Wen‐Bo
  organization: Xiamen University
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  givenname: Xin‐Yu
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  fullname: Xiao, Xin‐Yu
  organization: Xiamen University
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  givenname: Qing
  surname: Sun
  fullname: Sun, Qing
  organization: Xiamen University
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  givenname: Bo
  surname: Zhou
  fullname: Zhou, Bo
  organization: Xiamen University
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  givenname: Xin‐Qi
  surname: Zhu
  fullname: Zhu, Xin‐Qi
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  fullname: Yan, Juan‐Zhu
  organization: Xiamen University
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  givenname: Long‐Wu
  surname: Ye
  fullname: Ye, Long‐Wu
  email: longwuye@xmu.edu.cn
  organization: Chinese Academy of Sciences
BackLink https://www.ncbi.nlm.nih.gov/pubmed/27936302$$D View this record in MEDLINE/PubMed
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Issue 2
Keywords PI-ACID CATALYSIS
PHENOL SYNTHESIS
ENANTIOSELECTIVE GOLD CATALYSIS
MOLECULAR COMPLEXITY
IDENTIFICATION
3+2 CYCLOADDITION
platinum
annulation
homogeneous catalysis
heterocycles
CARBENES
ynamides
CYCLOISOMERIZATION
CYCLIZATION
Language English
License http://onlinelibrary.wiley.com/termsAndConditions#vor
2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Notes These authors contributed equally.
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Snippet Platinum‐catalyzed formal [5+2] and [4+2] annulations of isoxazoles with heterosubstituted alkynes enabled the atom‐economical synthesis of valuable...
Platinum-catalyzed formal [5+2] and [4+2] annulations of isoxazoles with heterosubstituted alkynes enabled the atom-economical synthesis of valuable...
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SubjectTerms Alkynes
annulation
Catalysis
Chemistry
Chemistry, Multidisciplinary
heterocycles
homogeneous catalysis
Intermediates
Physical Sciences
Platinum
Science & Technology
ynamides
Title Highly Site Selective Formal [5+2] and [4+2] Annulations of Isoxazoles with Heterosubstituted Alkynes by Platinum Catalysis: Rapid Access to Functionalized 1,3‐Oxazepines and 2,5‐Dihydropyridines
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