peri-Interaction between diarylmethyl and diarylmethylium units in 1,8-disubstituted naphthalenes: Preference of localized structure for the C-H bridged carbocation

Hidetoshi Kawai; Takayuki Nagasu; Takashi Takeda; Kenshu Fujiwara; Takashi Tsuji; Masakazu Ohkita; Jun Ichi Nishida; Takanori Suzuki

doi:10.1016/j.tetlet.2004.04.002

peri-Interaction between diarylmethyl and diarylmethylium units in 1,8-disubstituted naphthalenes: Preference of localized structure for the C-H bridged carbocation

Hidetoshi Kawai, Takayuki Nagasu, Takashi Takeda, Kenshu Fujiwara, Takashi Tsuji, Masakazu Ohkita, Jun Ichi Nishida, Takanori Suzuki

Research output: Contribution to journal › Article › peer-review

26 Citations (Scopus)

Abstract

(8-Diarylmethyl-1-naphthyl)bis(4-dimethylaminophenyl)methyliums (aryl=C₆H₅, 4-IC₆H₄, and 4-MeOC ₆H₄) were generated by hydride shift from (4-dimethylaminophenyl)methyl group to the diarylmethylium unit at peri-positions of naphthalene. Successful isolation and low-temperature X-ray analysis indicated that they are novel C-H bridged carbocations, which prefer the localized structure with a short contact of C-H⋯C⁺ rather than the delocalized one with a three-centered-two-electron bond of (C⋯H⋯C)⁺.

Original language	English
Pages (from-to)	4553-4558
Number of pages	6
Journal	Tetrahedron Letters
Volume	45
Issue number	23
DOIs	https://doi.org/10.1016/j.tetlet.2004.04.002
Publication status	Published - 2004 May 31
Externally published	Yes

Keywords

Carbocation
Hydride shift
Three-centered-two-electron bond
Triarylmethylium
peri-Interaction

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tetlet.2004.04.002

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@article{5b89c667ec4f448c83de302a10cbc65c,

title = "peri-Interaction between diarylmethyl and diarylmethylium units in 1,8-disubstituted naphthalenes: Preference of localized structure for the C-H bridged carbocation",

abstract = "(8-Diarylmethyl-1-naphthyl)bis(4-dimethylaminophenyl)methyliums (aryl=C6H5, 4-IC6H4, and 4-MeOC 6H4) were generated by hydride shift from (4-dimethylaminophenyl)methyl group to the diarylmethylium unit at peri-positions of naphthalene. Successful isolation and low-temperature X-ray analysis indicated that they are novel C-H bridged carbocations, which prefer the localized structure with a short contact of C-H⋯C+ rather than the delocalized one with a three-centered-two-electron bond of (C⋯H⋯C)+.",

keywords = "Carbocation, Hydride shift, Three-centered-two-electron bond, Triarylmethylium, peri-Interaction",

author = "Hidetoshi Kawai and Takayuki Nagasu and Takashi Takeda and Kenshu Fujiwara and Takashi Tsuji and Masakazu Ohkita and Nishida, {Jun Ichi} and Takanori Suzuki",

note = "Funding Information: This work was supported by the Ministry of Education, Science, and Culture, Japan (No. 15350019 and 14654139). We thank Prof. Tamotsu Inabe (Hokkaido University) for use of the X-ray structure analysis system. MS spectra were measured by Mr. Kenji Watanabe and Dr. Eri Fukushi at the GC–MS & NMR Laboratory (Faculty of Agriculture, Hokkaido University).",

year = "2004",

month = may,

day = "31",

doi = "10.1016/j.tetlet.2004.04.002",

language = "English",

volume = "45",

pages = "4553--4558",

journal = "Tetrahedron Letters",

issn = "0040-4039",

publisher = "Elsevier Limited",

number = "23",

}

TY - JOUR

T1 - peri-Interaction between diarylmethyl and diarylmethylium units in 1,8-disubstituted naphthalenes

T2 - Preference of localized structure for the C-H bridged carbocation

AU - Kawai, Hidetoshi

AU - Nagasu, Takayuki

AU - Takeda, Takashi

AU - Fujiwara, Kenshu

AU - Tsuji, Takashi

AU - Ohkita, Masakazu

AU - Nishida, Jun Ichi

AU - Suzuki, Takanori

N1 - Funding Information: This work was supported by the Ministry of Education, Science, and Culture, Japan (No. 15350019 and 14654139). We thank Prof. Tamotsu Inabe (Hokkaido University) for use of the X-ray structure analysis system. MS spectra were measured by Mr. Kenji Watanabe and Dr. Eri Fukushi at the GC–MS & NMR Laboratory (Faculty of Agriculture, Hokkaido University).

PY - 2004/5/31

Y1 - 2004/5/31

N2 - (8-Diarylmethyl-1-naphthyl)bis(4-dimethylaminophenyl)methyliums (aryl=C6H5, 4-IC6H4, and 4-MeOC 6H4) were generated by hydride shift from (4-dimethylaminophenyl)methyl group to the diarylmethylium unit at peri-positions of naphthalene. Successful isolation and low-temperature X-ray analysis indicated that they are novel C-H bridged carbocations, which prefer the localized structure with a short contact of C-H⋯C+ rather than the delocalized one with a three-centered-two-electron bond of (C⋯H⋯C)+.

AB - (8-Diarylmethyl-1-naphthyl)bis(4-dimethylaminophenyl)methyliums (aryl=C6H5, 4-IC6H4, and 4-MeOC 6H4) were generated by hydride shift from (4-dimethylaminophenyl)methyl group to the diarylmethylium unit at peri-positions of naphthalene. Successful isolation and low-temperature X-ray analysis indicated that they are novel C-H bridged carbocations, which prefer the localized structure with a short contact of C-H⋯C+ rather than the delocalized one with a three-centered-two-electron bond of (C⋯H⋯C)+.

KW - Carbocation

KW - Hydride shift

KW - Three-centered-two-electron bond

KW - Triarylmethylium

KW - peri-Interaction

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DO - 10.1016/j.tetlet.2004.04.002

M3 - Article

AN - SCOPUS:2442536187

SN - 0040-4039

VL - 45

SP - 4553

EP - 4558

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 23

ER -

peri-Interaction between diarylmethyl and diarylmethylium units in 1,8-disubstituted naphthalenes: Preference of localized structure for the C-H bridged carbocation

Abstract

Keywords

ASJC Scopus subject areas

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