Trimethylsumanene: Enantioselective synthesis, substituent effect on bowl structure, inversion energy, and electron conductivity

Shuhei Higashibayashi, Ryoji Tsuruoka, Yarasi Soujanya, Uppula Purushotham, G. Narahari Sastry, Shu Seki, Takeharu Ishikawa, Shinji Toyota, Hidehiro Sakurai

研究成果: Article

60 引用 (Scopus)

抄録

C 3 symmetric chiral trimethylsumanene was enantioselectively synthesized through Pd-catalyzed syn-selective cyclotrimerization of an enantiomerically pure iodonorbornenone, ring-opening/closing olefin metathesis, and oxidative aromatization where the sp 3 stereogenic center was transmitted to the bowl chirality. Chiral HPLC analysis/resolution of the derivatives were also achieved. Based on theoretical calculations, the columnar crystal packing structure of sumanene and trimethylsumanene was interpreted as due to attractive electrostatic or CH-π interaction. According to the experimental and theoretical studies, the bowl depth and inversion energy were found to increase on methylation for sumanene in contrast to corannulene. Dissimilarities of the effect of methylation on the bowl structure and inversion energy of sumanene and corannulene were ascribed to differences in steric repulsion. A double-well potential model was fitted to the bowl structureinversion energy correlation of substituted sumanenes, with a small deviation. The effects of various substituents on the sumanene structure and bowl-inversion energy were analyzed by density functional theory calculations, and it was shown that the bowl rigidity is controlled by a combination of electronic and steric effects of the substituents. The electron conductivity of trimethylsumanene was investigated by time-resolved microwave conductivity method, compared with that of sumanene.

元の言語English
ページ(範囲)450-467
ページ数18
ジャーナルBulletin of the Chemical Society of Japan
85
発行部数4
DOI
出版物ステータスPublished - 2012
外部発表Yes

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Electrons
Methylation
Aromatization
Chirality
Alkenes
Rigidity
Density functional theory
Electrostatics
Microwaves
sumanene
Derivatives
Crystals
corannulene

ASJC Scopus subject areas

  • Chemistry(all)

これを引用

Trimethylsumanene : Enantioselective synthesis, substituent effect on bowl structure, inversion energy, and electron conductivity. / Higashibayashi, Shuhei; Tsuruoka, Ryoji; Soujanya, Yarasi; Purushotham, Uppula; Sastry, G. Narahari; Seki, Shu; Ishikawa, Takeharu; Toyota, Shinji; Sakurai, Hidehiro.

:: Bulletin of the Chemical Society of Japan, 巻 85, 番号 4, 2012, p. 450-467.

研究成果: Article

Higashibayashi, Shuhei ; Tsuruoka, Ryoji ; Soujanya, Yarasi ; Purushotham, Uppula ; Sastry, G. Narahari ; Seki, Shu ; Ishikawa, Takeharu ; Toyota, Shinji ; Sakurai, Hidehiro. / Trimethylsumanene : Enantioselective synthesis, substituent effect on bowl structure, inversion energy, and electron conductivity. :: Bulletin of the Chemical Society of Japan. 2012 ; 巻 85, 番号 4. pp. 450-467.
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T2 - Enantioselective synthesis, substituent effect on bowl structure, inversion energy, and electron conductivity

AU - Higashibayashi, Shuhei

AU - Tsuruoka, Ryoji

AU - Soujanya, Yarasi

AU - Purushotham, Uppula

AU - Sastry, G. Narahari

AU - Seki, Shu

AU - Ishikawa, Takeharu

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AU - Sakurai, Hidehiro

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