Strategic use of nitrogen free radicals in natural product synthesis: Total synthesis of agelastatin A

Research output: Contribution to journalArticle

Abstract

The present review describes our endeavor to access agelastatin alkaloids wherein new means of radical nitrogenation of carbon-carbon double bonds have been developed. The first topic presents the development of intramolecular iron (II)-mediated radical aminohalogenation reactions of allyl azido formates and allyl N-tosyloxy carbamates, which culminated in the establishment of the 2nd- A nd 3rd-generation approaches to (-)-agelastatin A (AA). The second topic deals with the radial azidation reaction of carbon-carbon double bond with KMnO4/BnEt3NCl/TMSN3, a new reagent that produces an azido radical, by which the 4th-generation synthesis of AA has been successfully accomplished.

Original languageEnglish
Pages (from-to)472-481
Number of pages10
JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume77
Issue number5
DOIs
Publication statusPublished - Jan 1 2019

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Biological Products
Free Radicals
Nitrogen
Carbon
Carbamates
Alkaloids
Iron
agelastatin A

Keywords

  • Azidation
  • Bioactive natural products
  • Fe(II) halides
  • Free radical
  • Permanganate
  • Total synthesis

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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abstract = "The present review describes our endeavor to access agelastatin alkaloids wherein new means of radical nitrogenation of carbon-carbon double bonds have been developed. The first topic presents the development of intramolecular iron (II)-mediated radical aminohalogenation reactions of allyl azido formates and allyl N-tosyloxy carbamates, which culminated in the establishment of the 2nd- A nd 3rd-generation approaches to (-)-agelastatin A (AA). The second topic deals with the radial azidation reaction of carbon-carbon double bond with KMnO4/BnEt3NCl/TMSN3, a new reagent that produces an azido radical, by which the 4th-generation synthesis of AA has been successfully accomplished.",
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AB - The present review describes our endeavor to access agelastatin alkaloids wherein new means of radical nitrogenation of carbon-carbon double bonds have been developed. The first topic presents the development of intramolecular iron (II)-mediated radical aminohalogenation reactions of allyl azido formates and allyl N-tosyloxy carbamates, which culminated in the establishment of the 2nd- A nd 3rd-generation approaches to (-)-agelastatin A (AA). The second topic deals with the radial azidation reaction of carbon-carbon double bond with KMnO4/BnEt3NCl/TMSN3, a new reagent that produces an azido radical, by which the 4th-generation synthesis of AA has been successfully accomplished.

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