Carbon-carbon and carbon-hydrogen bond transformations mediated by highly reactive radicals and their application to the synthesis of bioactive compounds

Takehiko Yoshimitsu, Hiroto Nagaoka, Tetsuaki Tanaka

Research output: Contribution to journalReview article

5 Citations (Scopus)

Abstract

Reactive free radicals have wide applications in organic synthesis due to their remarkable chemical properties that allow useful molecular transformations. The present review covers the author's recent studies on the utilization of radical species in chemical synthesis of organic molecules: The first topic deals with two types of alkoxyl radicals (primary or tertiary) that selectively undergo dehydrogenation or β-scission to give rise to the key structural elements of (-)-CP-263,114, a ras-farnesyl transferase inhibitor. The second part of this review describes the development of new carbon-carbon bond forming reactions that proceed via the direct and selective abstraction of the hydrogen from the sp3C-H bond adjacent to oxygen or nitrogen. In this radical C-H bond transformation, triethylborane serves not only as a source of hydrogen abstractor but as an alkoxyl radical scavenger that enables the irreversible addition of carbon radicals to carbon-oxygen double bonds.

Original languageEnglish
Pages (from-to)665-675
Number of pages11
JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume65
Issue number7
Publication statusPublished - Jul 2007
Externally publishedYes

Fingerprint

Hydrogen bonds
Carbon
Hydrogen
Oxygen
Dehydrogenation
Transferases
Chemical properties
Free Radicals
Nitrogen
Molecules
alkoxyl radical

Keywords

  • β-amino alcohols
  • β-scission
  • (-)-CP-263,114 (Phomoidride B)
  • Alkoxyl radicals
  • C-H hydroxyalkylation
  • C-H transformations
  • Free radicals
  • Hydrogen abstraction
  • Tertiary nitrogen compounds
  • Total synthesis
  • Triethylborane

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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abstract = "Reactive free radicals have wide applications in organic synthesis due to their remarkable chemical properties that allow useful molecular transformations. The present review covers the author's recent studies on the utilization of radical species in chemical synthesis of organic molecules: The first topic deals with two types of alkoxyl radicals (primary or tertiary) that selectively undergo dehydrogenation or β-scission to give rise to the key structural elements of (-)-CP-263,114, a ras-farnesyl transferase inhibitor. The second part of this review describes the development of new carbon-carbon bond forming reactions that proceed via the direct and selective abstraction of the hydrogen from the sp3C-H bond adjacent to oxygen or nitrogen. In this radical C-H bond transformation, triethylborane serves not only as a source of hydrogen abstractor but as an alkoxyl radical scavenger that enables the irreversible addition of carbon radicals to carbon-oxygen double bonds.",
keywords = "β-amino alcohols, β-scission, (-)-CP-263,114 (Phomoidride B), Alkoxyl radicals, C-H hydroxyalkylation, C-H transformations, Free radicals, Hydrogen abstraction, Tertiary nitrogen compounds, Total synthesis, Triethylborane",
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T1 - Carbon-carbon and carbon-hydrogen bond transformations mediated by highly reactive radicals and their application to the synthesis of bioactive compounds

AU - Yoshimitsu, Takehiko

AU - Nagaoka, Hiroto

AU - Tanaka, Tetsuaki

PY - 2007/7

Y1 - 2007/7

N2 - Reactive free radicals have wide applications in organic synthesis due to their remarkable chemical properties that allow useful molecular transformations. The present review covers the author's recent studies on the utilization of radical species in chemical synthesis of organic molecules: The first topic deals with two types of alkoxyl radicals (primary or tertiary) that selectively undergo dehydrogenation or β-scission to give rise to the key structural elements of (-)-CP-263,114, a ras-farnesyl transferase inhibitor. The second part of this review describes the development of new carbon-carbon bond forming reactions that proceed via the direct and selective abstraction of the hydrogen from the sp3C-H bond adjacent to oxygen or nitrogen. In this radical C-H bond transformation, triethylborane serves not only as a source of hydrogen abstractor but as an alkoxyl radical scavenger that enables the irreversible addition of carbon radicals to carbon-oxygen double bonds.

AB - Reactive free radicals have wide applications in organic synthesis due to their remarkable chemical properties that allow useful molecular transformations. The present review covers the author's recent studies on the utilization of radical species in chemical synthesis of organic molecules: The first topic deals with two types of alkoxyl radicals (primary or tertiary) that selectively undergo dehydrogenation or β-scission to give rise to the key structural elements of (-)-CP-263,114, a ras-farnesyl transferase inhibitor. The second part of this review describes the development of new carbon-carbon bond forming reactions that proceed via the direct and selective abstraction of the hydrogen from the sp3C-H bond adjacent to oxygen or nitrogen. In this radical C-H bond transformation, triethylborane serves not only as a source of hydrogen abstractor but as an alkoxyl radical scavenger that enables the irreversible addition of carbon radicals to carbon-oxygen double bonds.

KW - β-amino alcohols

KW - β-scission

KW - (-)-CP-263,114 (Phomoidride B)

KW - Alkoxyl radicals

KW - C-H hydroxyalkylation

KW - C-H transformations

KW - Free radicals

KW - Hydrogen abstraction

KW - Tertiary nitrogen compounds

KW - Total synthesis

KW - Triethylborane

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M3 - Review article

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VL - 65

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JO - Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry

JF - Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry

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