Enantioselective Synthesis of Nine- to Eleven-Membered Cyclic Polyphenylenes Containing Heteroatoms by Catalytic Intramolecular [2+2+2] Cycloaddition

Takanori Shibata, Toru Fusamae, Hideaki Takano, Natsuhiko Sugimura, Stephen Kyalo Kanyiva

Research output: Contribution to journalArticle

Abstract

Rh-catalyzed enantioselective intramolecular reactions of triynes consisting of 1,6-diyne and 1,10-diyne moieties tethered by sulfur or oxygen and ortho-phenylene moieties proceeded to give chiral tetrabenzoheteronines possessing a nine-membered ring system as [2+2+2] cycloadducts. In the reaction of triynes consisting of 1,6-diyne and 1,11-diyne moieties, sulfur-tethered substrates gave chiral metacyclophanes with an eleven-membered ring system, whereas an oxygen- and sulfur-tethered substrate afforded a tetrabenzo-1,4-oxathiecine with a ten-membered ring system. The mechanisms of the different reaction pathways depending on the heteroatom of the tether are discussed.

Original languageEnglish
JournalAsian Journal of Organic Chemistry
DOIs
Publication statusPublished - 2019 Jan 1

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Cycloaddition
Sulfur
Oxygen
Substrates

Keywords

  • axial chirality
  • cycloaddition
  • enantioselectivity
  • heterocycles
  • medium ring system

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Enantioselective Synthesis of Nine- to Eleven-Membered Cyclic Polyphenylenes Containing Heteroatoms by Catalytic Intramolecular [2+2+2] Cycloaddition",
abstract = "Rh-catalyzed enantioselective intramolecular reactions of triynes consisting of 1,6-diyne and 1,10-diyne moieties tethered by sulfur or oxygen and ortho-phenylene moieties proceeded to give chiral tetrabenzoheteronines possessing a nine-membered ring system as [2+2+2] cycloadducts. In the reaction of triynes consisting of 1,6-diyne and 1,11-diyne moieties, sulfur-tethered substrates gave chiral metacyclophanes with an eleven-membered ring system, whereas an oxygen- and sulfur-tethered substrate afforded a tetrabenzo-1,4-oxathiecine with a ten-membered ring system. The mechanisms of the different reaction pathways depending on the heteroatom of the tether are discussed.",
keywords = "axial chirality, cycloaddition, enantioselectivity, heterocycles, medium ring system",
author = "Takanori Shibata and Toru Fusamae and Hideaki Takano and Natsuhiko Sugimura and Kanyiva, {Stephen Kyalo}",
year = "2019",
month = "1",
day = "1",
doi = "10.1002/ajoc.201900051",
language = "English",
journal = "Asian Journal of Organic Chemistry",
issn = "2193-5807",
publisher = "Wiley - VCH Verlag GmbH & CO. KGaA",

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TY - JOUR

T1 - Enantioselective Synthesis of Nine- to Eleven-Membered Cyclic Polyphenylenes Containing Heteroatoms by Catalytic Intramolecular [2+2+2] Cycloaddition

AU - Shibata, Takanori

AU - Fusamae, Toru

AU - Takano, Hideaki

AU - Sugimura, Natsuhiko

AU - Kanyiva, Stephen Kyalo

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Rh-catalyzed enantioselective intramolecular reactions of triynes consisting of 1,6-diyne and 1,10-diyne moieties tethered by sulfur or oxygen and ortho-phenylene moieties proceeded to give chiral tetrabenzoheteronines possessing a nine-membered ring system as [2+2+2] cycloadducts. In the reaction of triynes consisting of 1,6-diyne and 1,11-diyne moieties, sulfur-tethered substrates gave chiral metacyclophanes with an eleven-membered ring system, whereas an oxygen- and sulfur-tethered substrate afforded a tetrabenzo-1,4-oxathiecine with a ten-membered ring system. The mechanisms of the different reaction pathways depending on the heteroatom of the tether are discussed.

AB - Rh-catalyzed enantioselective intramolecular reactions of triynes consisting of 1,6-diyne and 1,10-diyne moieties tethered by sulfur or oxygen and ortho-phenylene moieties proceeded to give chiral tetrabenzoheteronines possessing a nine-membered ring system as [2+2+2] cycloadducts. In the reaction of triynes consisting of 1,6-diyne and 1,11-diyne moieties, sulfur-tethered substrates gave chiral metacyclophanes with an eleven-membered ring system, whereas an oxygen- and sulfur-tethered substrate afforded a tetrabenzo-1,4-oxathiecine with a ten-membered ring system. The mechanisms of the different reaction pathways depending on the heteroatom of the tether are discussed.

KW - axial chirality

KW - cycloaddition

KW - enantioselectivity

KW - heterocycles

KW - medium ring system

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