Dithieno[3,4-b:3′,4′-d]thiophene-Annelated Antiaromatic Planar Cyclooctatetraene with Olefinic Protons

被引：29

作者：

Aita, Kazunari ^{[1
]}

Ohmae, Takeshi ^{[1
]}

Takase, Masayoshi ^{[1
]}

Nomura, Kotohiro ^{[1
]}

Kimura, Hideaki ^{[2
]}

Nishinage, Tohru ^{[1
]}

机构：

[1] Tokyo Metropolitan Univ, Dept Chem, Grad Sch Sci & Engn, Hachioji, Tokyo 1920397, Japan

[2] Bruker BioSpin KK, Kanagawa Ku, Yokohama, Kanagawa 2210022, Japan

来源：

ORGANIC LETTERS | 2013年 / 15卷 / 14期

关键词：

CHEMICAL-SHIFTS NICS; RING CURRENTS; PORPHYRIN SHEET; AROMATICITY; DIMETHYLDIHYDROPYRENE; HYDROCARBON; BENZENE; NUCLEUS; SYSTEM; UNITS;

D O I：

10.1021/ol401125f

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The design and synthesis of a new planar cyclooctatetraene (COT) with protons directly connected to the COT ring was attained by mono-annelation with dithieno[3,4-b:3',4'-d]thiophene. The planar structure of the COT core was unambiguously confirmed by X-ray crystallography. The magnetic antiaromaticity of the COT core was found to be higher than that of the previously synthesized planar COTs with olefinic protons, according to the results of H-1 NMR and absorption spectra as well as NICS calculations.

引用

页码：3522 / 3525

页数：4

共 32 条

[1] Nucleus-independent chemical shifts (NICS) as an aromaticity criterion [J].

Chen, ZF ;

Wannere, CS ;

Corminboeuf, C ;

Puchta, R ;

Schleyer, PV .

CHEMICAL REVIEWS, 2005, 105 (10) :3842-3888

[2] Ipsocentric ring currents in density functional theory [J].

Havenith, Remco W. A. ;

Fowler, Patrick W. .

CHEMICAL PHYSICS LETTERS, 2007, 449 (4-6) :347-353

[3] Aromaticity and Antiaromaticity in the Low-Lying Electronic States of Cyclooctatetraene [J].

Karadakov, Peter B. .

JOURNAL OF PHYSICAL CHEMISTRY A, 2008, 112 (49) :12707-12713

[4]

Klärner FG, 2001, ANGEW CHEM INT EDIT, V40, P3977, DOI 10.1002/1521-3773(20011105)40:21<3977::AID-ANIE3977>3.0.CO

[5]

2-N

[6] Efficient synthesis of benzene and planar cyclooctatetraene fully annelated with bicyclo[2.1.1]hex-2-ene [J].

Matsuura, A ;

Komatsu, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (08) :1768-1769

[7] An experimental estimate of the relative aromaticity of the cyclooctatetraene dianion by fusion to dimethyldihydropyrene [J].

Mitchell, Reginald H. ;

Zhang, Pengrong ;

Berg, David J. ;

Williams, Richard Vaughan .

CHEMICAL COMMUNICATIONS, 2012, 48 (65) :8144-8146

[8]

Mouri K., 2012, ANGEW CHEM, V124, P6073

[9] A directly fused tetrameric porphyrin sheet and its anomalous electronic properties that arise from the planar cyclooctatetraene core [J].

Nakamura, Y ;

Aratani, N ;

Shinokubo, H ;

Takagi, A ;

Kawai, T ;

Matsumoto, T ;

Yoon, ZS ;

Kim, DY ;

Ahn, TK ;

Kim, D ;

Muranaka, A ;

Kobayashi, N ;

Osuka, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (12) :4119-4127

[10] Synthesis and characterizations of free base and Cu(II) complex of a porphyrin sheet [J].

Nakamura, Yasuyuki ;

Aratani, Naoki ;

Furukawa, Ko ;

Osuka, Atsuhiro .

TETRAHEDRON, 2008, 64 (50) :11433-11439

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