Chain Walking as a Strategy for Carbon-Carbon Bond Formation at Unreactive Sites in Organic Synthesis: Catalytic Cycloisomerization of Various 1,n-Dienes

Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, Fumitoshi Kakiuchi, Takuya Kochi

研究成果: Article

36 引用 (Scopus)

抄録

Carbon-carbon bond formation at unreactive sp3-carbons in small organic molecules via chain walking was achieved for the palladium-catalyzed cycloisomerization of 1,n-dienes. Various 1,n-dienes (n = 7-14) such as those containing cyclic alkenes, acyclic internal alkenes, and a trisubstituted alkene can be used for the chain-walking cycloisomerization/hydrogenation process, and five-membered ring compounds including simple cyclopentane and pyrrolidine derivatives can easily be prepared. Chain walking over a tertiary carbon was also found to be possible in the cycloisomerization. It is not necessary for the linker portion of the diene to contain a quaternary center, and diene substrates with two alkene moieties linked by a tertiary carbon or a nitrogen atom can also be used as substrates. Column chromatography using silica gel containing silver nitrate was found to be effective for isolating some of the cycloisomerization products without hydrogenation. Deuterium-labeling experiments provided direct evidence to show that the reaction proceeds via a chain-walking mechanism.

元の言語English
ページ(範囲)16163-16171
ページ数9
ジャーナルJournal of the American Chemical Society
137
発行部数51
DOI
出版物ステータスPublished - 2015 12 30

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Synthetic Chemistry Techniques
Walking
Carbon
Olefins
Alkenes
Hydrogenation
Cycloparaffins
Cyclopentanes
Silver Nitrate
Column chromatography
Deuterium
Silica Gel
Palladium
Silica gel
Substrates
Labeling
Chromatography
Nitrates
Silver
Nitrogen

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

これを引用

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abstract = "Carbon-carbon bond formation at unreactive sp3-carbons in small organic molecules via chain walking was achieved for the palladium-catalyzed cycloisomerization of 1,n-dienes. Various 1,n-dienes (n = 7-14) such as those containing cyclic alkenes, acyclic internal alkenes, and a trisubstituted alkene can be used for the chain-walking cycloisomerization/hydrogenation process, and five-membered ring compounds including simple cyclopentane and pyrrolidine derivatives can easily be prepared. Chain walking over a tertiary carbon was also found to be possible in the cycloisomerization. It is not necessary for the linker portion of the diene to contain a quaternary center, and diene substrates with two alkene moieties linked by a tertiary carbon or a nitrogen atom can also be used as substrates. Column chromatography using silica gel containing silver nitrate was found to be effective for isolating some of the cycloisomerization products without hydrogenation. Deuterium-labeling experiments provided direct evidence to show that the reaction proceeds via a chain-walking mechanism.",
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T2 - Catalytic Cycloisomerization of Various 1,n-Dienes

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AU - Aoyama, Yuka

AU - Kawasaki, Junichi

AU - Kakiuchi, Fumitoshi

AU - Kochi, Takuya

PY - 2015/12/30

Y1 - 2015/12/30

N2 - Carbon-carbon bond formation at unreactive sp3-carbons in small organic molecules via chain walking was achieved for the palladium-catalyzed cycloisomerization of 1,n-dienes. Various 1,n-dienes (n = 7-14) such as those containing cyclic alkenes, acyclic internal alkenes, and a trisubstituted alkene can be used for the chain-walking cycloisomerization/hydrogenation process, and five-membered ring compounds including simple cyclopentane and pyrrolidine derivatives can easily be prepared. Chain walking over a tertiary carbon was also found to be possible in the cycloisomerization. It is not necessary for the linker portion of the diene to contain a quaternary center, and diene substrates with two alkene moieties linked by a tertiary carbon or a nitrogen atom can also be used as substrates. Column chromatography using silica gel containing silver nitrate was found to be effective for isolating some of the cycloisomerization products without hydrogenation. Deuterium-labeling experiments provided direct evidence to show that the reaction proceeds via a chain-walking mechanism.

AB - Carbon-carbon bond formation at unreactive sp3-carbons in small organic molecules via chain walking was achieved for the palladium-catalyzed cycloisomerization of 1,n-dienes. Various 1,n-dienes (n = 7-14) such as those containing cyclic alkenes, acyclic internal alkenes, and a trisubstituted alkene can be used for the chain-walking cycloisomerization/hydrogenation process, and five-membered ring compounds including simple cyclopentane and pyrrolidine derivatives can easily be prepared. Chain walking over a tertiary carbon was also found to be possible in the cycloisomerization. It is not necessary for the linker portion of the diene to contain a quaternary center, and diene substrates with two alkene moieties linked by a tertiary carbon or a nitrogen atom can also be used as substrates. Column chromatography using silica gel containing silver nitrate was found to be effective for isolating some of the cycloisomerization products without hydrogenation. Deuterium-labeling experiments provided direct evidence to show that the reaction proceeds via a chain-walking mechanism.

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