Enantioselective synthesis of chiral buckybowl and chiral azabuckybowl

Research output: Contribution to journalReview article

4 Citations (Scopus)

Abstract

Buckybowls are bowl-shaped aromatic hydrocarbons corresponding to a partial fullerene structure or a cap structure of carbon nanotubes. Since the discovery of C60 fullerene in 1985, buckybowls have attracted much attention due to their physical properties, not only as model compounds for fullerenes, but also as unique bowl-shaped aromatic compounds. We have achieved first enantioselective synthesis of chiral buckybowl, trimethylsumanene, and chiral azabuckybowl, triazasumanene. To achieve the synthesis, we have developed Pd-catalyzed syn- selective cyclotrimerization of enantiopure iodonorbornene derivatives, giving enantiopure C3 symmetric syw-tris(norborneno) benzenes. By using syw-tris(norborneno)benzene derivatives as synthetic intermediates, trimethylsumanene and triazasumanene were synthesized featuring tandem ring-opening/closing metathesis reaction or amide recombination reaction and oxidative aromatization. From the racemization experiments, the bowl inversion/racemization energies of trimethylsumanene and triazasumanene were determined to be 21.6 kcal/mol and 42.2 kcal/mol, respectively.

Original languageEnglish
Pages (from-to)26-38
Number of pages13
JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume72
Issue number1
DOIs
Publication statusPublished - 2014
Externally publishedYes

Fingerprint

Fullerenes
Benzene Derivatives
Aromatization
Aromatic Hydrocarbons
Carbon Nanotubes
Aromatic compounds
Benzene
Amides
Physical properties
Derivatives
Experiments
fullerene C60

Keywords

  • Azabuckybowl
  • Bowl chirality
  • Bowl inversion
  • Buckybowl
  • Chiral buckybowl
  • Enantioselective synthesis
  • Racemization

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

@article{b37739326ee34377a0d956affe482f12,
title = "Enantioselective synthesis of chiral buckybowl and chiral azabuckybowl",
abstract = "Buckybowls are bowl-shaped aromatic hydrocarbons corresponding to a partial fullerene structure or a cap structure of carbon nanotubes. Since the discovery of C60 fullerene in 1985, buckybowls have attracted much attention due to their physical properties, not only as model compounds for fullerenes, but also as unique bowl-shaped aromatic compounds. We have achieved first enantioselective synthesis of chiral buckybowl, trimethylsumanene, and chiral azabuckybowl, triazasumanene. To achieve the synthesis, we have developed Pd-catalyzed syn- selective cyclotrimerization of enantiopure iodonorbornene derivatives, giving enantiopure C3 symmetric syw-tris(norborneno) benzenes. By using syw-tris(norborneno)benzene derivatives as synthetic intermediates, trimethylsumanene and triazasumanene were synthesized featuring tandem ring-opening/closing metathesis reaction or amide recombination reaction and oxidative aromatization. From the racemization experiments, the bowl inversion/racemization energies of trimethylsumanene and triazasumanene were determined to be 21.6 kcal/mol and 42.2 kcal/mol, respectively.",
keywords = "Azabuckybowl, Bowl chirality, Bowl inversion, Buckybowl, Chiral buckybowl, Enantioselective synthesis, Racemization",
author = "Shuhei Higashibayashi",
year = "2014",
doi = "10.5059/yukigoseikyokaishi.72.26",
language = "English",
volume = "72",
pages = "26--38",
journal = "Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry",
issn = "0037-9980",
publisher = "Society of Synthetic Organic Chemistry",
number = "1",

}

TY - JOUR

T1 - Enantioselective synthesis of chiral buckybowl and chiral azabuckybowl

AU - Higashibayashi, Shuhei

PY - 2014

Y1 - 2014

N2 - Buckybowls are bowl-shaped aromatic hydrocarbons corresponding to a partial fullerene structure or a cap structure of carbon nanotubes. Since the discovery of C60 fullerene in 1985, buckybowls have attracted much attention due to their physical properties, not only as model compounds for fullerenes, but also as unique bowl-shaped aromatic compounds. We have achieved first enantioselective synthesis of chiral buckybowl, trimethylsumanene, and chiral azabuckybowl, triazasumanene. To achieve the synthesis, we have developed Pd-catalyzed syn- selective cyclotrimerization of enantiopure iodonorbornene derivatives, giving enantiopure C3 symmetric syw-tris(norborneno) benzenes. By using syw-tris(norborneno)benzene derivatives as synthetic intermediates, trimethylsumanene and triazasumanene were synthesized featuring tandem ring-opening/closing metathesis reaction or amide recombination reaction and oxidative aromatization. From the racemization experiments, the bowl inversion/racemization energies of trimethylsumanene and triazasumanene were determined to be 21.6 kcal/mol and 42.2 kcal/mol, respectively.

AB - Buckybowls are bowl-shaped aromatic hydrocarbons corresponding to a partial fullerene structure or a cap structure of carbon nanotubes. Since the discovery of C60 fullerene in 1985, buckybowls have attracted much attention due to their physical properties, not only as model compounds for fullerenes, but also as unique bowl-shaped aromatic compounds. We have achieved first enantioselective synthesis of chiral buckybowl, trimethylsumanene, and chiral azabuckybowl, triazasumanene. To achieve the synthesis, we have developed Pd-catalyzed syn- selective cyclotrimerization of enantiopure iodonorbornene derivatives, giving enantiopure C3 symmetric syw-tris(norborneno) benzenes. By using syw-tris(norborneno)benzene derivatives as synthetic intermediates, trimethylsumanene and triazasumanene were synthesized featuring tandem ring-opening/closing metathesis reaction or amide recombination reaction and oxidative aromatization. From the racemization experiments, the bowl inversion/racemization energies of trimethylsumanene and triazasumanene were determined to be 21.6 kcal/mol and 42.2 kcal/mol, respectively.

KW - Azabuckybowl

KW - Bowl chirality

KW - Bowl inversion

KW - Buckybowl

KW - Chiral buckybowl

KW - Enantioselective synthesis

KW - Racemization

UR - http://www.scopus.com/inward/record.url?scp=84898425652&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84898425652&partnerID=8YFLogxK

U2 - 10.5059/yukigoseikyokaishi.72.26

DO - 10.5059/yukigoseikyokaishi.72.26

M3 - Review article

AN - SCOPUS:84898425652

VL - 72

SP - 26

EP - 38

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

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

SN - 0037-9980

IS - 1

ER -