Divergent, Strain-Release Reactions of Azabicyclo[1.1.0]butyl Carbinols : Semipinacol or Spiroepoxy Azetidine Formation
© 2021 Wiley-VCH GmbH..
The azetidine moiety is a privileged motif in medicinal chemistry and new methods that access them efficiently are highly sought after. Towards this goal, we have found that azabicyclo[1.1.0]butyl carbinols, readily obtained from the highly strained azabicyclo[1.1.0]butane (ABB), can undergo divergent strain-release reactions upon N-activation. Treatment with trifluoroacetic anhydride or triflic anhydride triggered a semipinacol rearrangement to give keto 1,3,3-substituted azetidines. More than 20 examples were explored, enabling us to evaluate selectivity and the migratory aptitude of different groups. Alternatively, treatment of the same alcohols with benzyl chloroformate in the presence of NaI led to iodohydrin intermediates which gave spiroepoxy azetidines upon treatment with base. The electronic nature of the activating agent dictates which pathway operates.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2021 |
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| Erschienen: |
2021 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:60 |
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| Enthalten in: |
Angewandte Chemie (International ed. in English) - 60(2021), 13 vom: 22. März, Seite 7360-7365 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Gregson, Charlotte H U [VerfasserIn] |
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| Links: |
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| Themen: |
Azabicyclo[1.1.0]butane |
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| Anmerkungen: |
Date Completed 06.04.2021 Date Revised 07.11.2023 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1002/anie.202100583 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM321156196 |
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| 500 | |a Date Revised 07.11.2023 | ||
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| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a © 2021 Wiley-VCH GmbH. | ||
| 520 | |a The azetidine moiety is a privileged motif in medicinal chemistry and new methods that access them efficiently are highly sought after. Towards this goal, we have found that azabicyclo[1.1.0]butyl carbinols, readily obtained from the highly strained azabicyclo[1.1.0]butane (ABB), can undergo divergent strain-release reactions upon N-activation. Treatment with trifluoroacetic anhydride or triflic anhydride triggered a semipinacol rearrangement to give keto 1,3,3-substituted azetidines. More than 20 examples were explored, enabling us to evaluate selectivity and the migratory aptitude of different groups. Alternatively, treatment of the same alcohols with benzyl chloroformate in the presence of NaI led to iodohydrin intermediates which gave spiroepoxy azetidines upon treatment with base. The electronic nature of the activating agent dictates which pathway operates | ||
| 650 | 4 | |a Journal Article | |
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| 650 | 4 | |a azabicyclo[1.1.0]butane | |
| 650 | 4 | |a azetidines | |
| 650 | 4 | |a epoxides | |
| 650 | 4 | |a ring expansion | |
| 650 | 4 | |a strained molecules | |
| 700 | 1 | |a Noble, Adam |e verfasserin |4 aut | |
| 700 | 1 | |a Aggarwal, Varinder K |e verfasserin |4 aut | |
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