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 in | Angewandte Chemie International Edition Vol. 56; no. 2; pp. 605 - 609 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
WEINHEIM
Wiley
09.01.2017
Wiley Subscription Services, Inc |
Edition | International 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. |
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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 – sequence: 2 givenname: Xin‐Yu surname: Xiao fullname: Xiao, Xin‐Yu organization: Xiamen University – sequence: 3 givenname: Qing surname: Sun fullname: Sun, Qing organization: Xiamen University – sequence: 4 givenname: Bo surname: Zhou fullname: Zhou, Bo organization: Xiamen University – sequence: 5 givenname: Xin‐Qi surname: Zhu fullname: Zhu, Xin‐Qi organization: Xiamen University – sequence: 6 givenname: Juan‐Zhu surname: Yan fullname: Yan, Juan‐Zhu organization: Xiamen University – sequence: 7 givenname: Xin surname: Lu fullname: Lu, Xin email: xinlu@xmu.edu.cn organization: Xiamen University – sequence: 8 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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Keywords | PI-ACID CATALYSIS PHENOL SYNTHESIS ENANTIOSELECTIVE GOLD CATALYSIS MOLECULAR COMPLEXITY IDENTIFICATION 3+2 CYCLOADDITION platinum annulation homogeneous catalysis heterocycles CARBENES ynamides CYCLOISOMERIZATION CYCLIZATION |
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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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