Internal-Edge-Substituted Coumarin-Fused [6]Helicenes

Asymmetric Synthesis, Structural Features, and Control of Self-Assembly

Kazuteru Usui, Kosuke Yamamoto, Yuhei Ueno, Kazunobu Igawa, Ryusuke Hagihara, Toshinobu Masuda, Akio Ojida, Satoru Karasawa, Katsuhiko Tomooka, Go Hirai, Hiroshi Suemune

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

π-Conjugated helicenes containing heteroatoms have attracted significant attention due to their diverse chemical and electronic structures, as well as tunable physical properties. It was rationally anticipated that the self-assembly of coumarin-fused helicenes would be controlled by the effects of a substituent on the internal edge of the helix. Here, this work reports the efficient syntheses of coumarin-fused helicenes 1 a,b (R=Ph, Me), and the enantioselective synthesis of 1 a (R=Ph) by chiral AuI-catalyzed hydroarylation. The helical structure of 1 was unambiguously determined by X-ray crystallography. Of particular note, the enantiomerically pure crystal of 1 a adopted a one-dimensional columnar structure based on π–π stacking interactions, as expected. Furthermore, a significant difference between the fluorescence quantum yields of the enantiomerically pure form and racemate of 1 a was observed.

Original languageEnglish
Pages (from-to)14617-14621
Number of pages5
JournalChemistry - A European Journal
Volume24
Issue number55
DOIs
Publication statusPublished - Oct 1 2018

Fingerprint

Self assembly
X ray crystallography
Quantum yield
Electronic structure
Physical properties
Fluorescence
Crystals
helicenes
coumarin

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Internal-Edge-Substituted Coumarin-Fused [6]Helicenes : Asymmetric Synthesis, Structural Features, and Control of Self-Assembly. / Usui, Kazuteru; Yamamoto, Kosuke; Ueno, Yuhei; Igawa, Kazunobu; Hagihara, Ryusuke; Masuda, Toshinobu; Ojida, Akio; Karasawa, Satoru; Tomooka, Katsuhiko; Hirai, Go; Suemune, Hiroshi.

In: Chemistry - A European Journal, Vol. 24, No. 55, 01.10.2018, p. 14617-14621.

Research output: Contribution to journalArticle

Usui, Kazuteru ; Yamamoto, Kosuke ; Ueno, Yuhei ; Igawa, Kazunobu ; Hagihara, Ryusuke ; Masuda, Toshinobu ; Ojida, Akio ; Karasawa, Satoru ; Tomooka, Katsuhiko ; Hirai, Go ; Suemune, Hiroshi. / Internal-Edge-Substituted Coumarin-Fused [6]Helicenes : Asymmetric Synthesis, Structural Features, and Control of Self-Assembly. In: Chemistry - A European Journal. 2018 ; Vol. 24, No. 55. pp. 14617-14621.
@article{87848f002add4138bba4bfdbbffa48fc,
title = "Internal-Edge-Substituted Coumarin-Fused [6]Helicenes: Asymmetric Synthesis, Structural Features, and Control of Self-Assembly",
abstract = "π-Conjugated helicenes containing heteroatoms have attracted significant attention due to their diverse chemical and electronic structures, as well as tunable physical properties. It was rationally anticipated that the self-assembly of coumarin-fused helicenes would be controlled by the effects of a substituent on the internal edge of the helix. Here, this work reports the efficient syntheses of coumarin-fused helicenes 1 a,b (R=Ph, Me), and the enantioselective synthesis of 1 a (R=Ph) by chiral AuI-catalyzed hydroarylation. The helical structure of 1 was unambiguously determined by X-ray crystallography. Of particular note, the enantiomerically pure crystal of 1 a adopted a one-dimensional columnar structure based on π–π stacking interactions, as expected. Furthermore, a significant difference between the fluorescence quantum yields of the enantiomerically pure form and racemate of 1 a was observed.",
author = "Kazuteru Usui and Kosuke Yamamoto and Yuhei Ueno and Kazunobu Igawa and Ryusuke Hagihara and Toshinobu Masuda and Akio Ojida and Satoru Karasawa and Katsuhiko Tomooka and Go Hirai and Hiroshi Suemune",
year = "2018",
month = "10",
day = "1",
doi = "10.1002/chem.201803270",
language = "English",
volume = "24",
pages = "14617--14621",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "55",

}

TY - JOUR

T1 - Internal-Edge-Substituted Coumarin-Fused [6]Helicenes

T2 - Asymmetric Synthesis, Structural Features, and Control of Self-Assembly

AU - Usui, Kazuteru

AU - Yamamoto, Kosuke

AU - Ueno, Yuhei

AU - Igawa, Kazunobu

AU - Hagihara, Ryusuke

AU - Masuda, Toshinobu

AU - Ojida, Akio

AU - Karasawa, Satoru

AU - Tomooka, Katsuhiko

AU - Hirai, Go

AU - Suemune, Hiroshi

PY - 2018/10/1

Y1 - 2018/10/1

N2 - π-Conjugated helicenes containing heteroatoms have attracted significant attention due to their diverse chemical and electronic structures, as well as tunable physical properties. It was rationally anticipated that the self-assembly of coumarin-fused helicenes would be controlled by the effects of a substituent on the internal edge of the helix. Here, this work reports the efficient syntheses of coumarin-fused helicenes 1 a,b (R=Ph, Me), and the enantioselective synthesis of 1 a (R=Ph) by chiral AuI-catalyzed hydroarylation. The helical structure of 1 was unambiguously determined by X-ray crystallography. Of particular note, the enantiomerically pure crystal of 1 a adopted a one-dimensional columnar structure based on π–π stacking interactions, as expected. Furthermore, a significant difference between the fluorescence quantum yields of the enantiomerically pure form and racemate of 1 a was observed.

AB - π-Conjugated helicenes containing heteroatoms have attracted significant attention due to their diverse chemical and electronic structures, as well as tunable physical properties. It was rationally anticipated that the self-assembly of coumarin-fused helicenes would be controlled by the effects of a substituent on the internal edge of the helix. Here, this work reports the efficient syntheses of coumarin-fused helicenes 1 a,b (R=Ph, Me), and the enantioselective synthesis of 1 a (R=Ph) by chiral AuI-catalyzed hydroarylation. The helical structure of 1 was unambiguously determined by X-ray crystallography. Of particular note, the enantiomerically pure crystal of 1 a adopted a one-dimensional columnar structure based on π–π stacking interactions, as expected. Furthermore, a significant difference between the fluorescence quantum yields of the enantiomerically pure form and racemate of 1 a was observed.

UR - http://www.scopus.com/inward/record.url?scp=85053440464&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85053440464&partnerID=8YFLogxK

U2 - 10.1002/chem.201803270

DO - 10.1002/chem.201803270

M3 - Article

VL - 24

SP - 14617

EP - 14621

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 55

ER -