Thiophene-Fused Bisdehydro[12]annulene That Undergoes Transannular Alkyne Cycloaddition by Either Light or Heat

被引：27

作者：

Fukazawa, Aiko ^{[1
]}

Oshima, Hiroya ^{[1
]}

Shiota, Yoshihito ^{[4
]}

Takahashi, Shouya ^{[4
]}

Yoshizawa, Kazunari ^{[4
]}

Yamaguchi, Shigehiro ^{[1
,2
,3
]}

机构：

[1] Nagoya Univ, Grad Sch Sci, Dept Chem, Chikusa Ku, Nagoya, Aichi 4648602, Japan

[2] Nagoya Univ, Res Ctr Mat Sci, Chikusa Ku, Nagoya, Aichi 4648602, Japan

[3] Nagoya Univ, Inst Transformat Biomol WPI ITbM, Chikusa Ku, Nagoya, Aichi 4648602, Japan

[4] Kyushu Univ, Inst Mat Chem & Engn, Nishi Ku, Fukuoka 8190395, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 05期

关键词：

MOLECULAR-ORBITAL METHODS; UNSATURATED MACROCYCLIC COMPOUNDS; ELECTRON-TRANSFER OXIDATION; GAUSSIAN-TYPE BASIS; TRIPLE BONDS; INTRAMOLECULAR INTERACTIONS; ORGANIC-MOLECULES; BIPHENYLENE; CONSTRUCTION; POLYMERIZATION;

D O I：

10.1021/ja3126849

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A new bisdehydro[12]annulene derivative having a thiophene-fused structure has been synthesized. This highly twisted pi-conjugated macrocycle with two acetylene moieties in close proximity produces a [2+2]-type alkyne cycloadduct by either photoirradiation or mild heating without any transition metals. Theoretical calculations reveal that the thermal reaction proceeds through successive 8 pi and 4 pi electrocyclic reactions, while the photochemical reaction is an asynchronous concerted [2+2] cycloaddition. The fused structure with the less-aromatic thiophene ring is crucial for achieving this reaction. The cycloadduct, thiophene-fused biphenylene, has significant potential as a new polycyclic pi-scaffold for electronic applications.

引用

页码：1731 / 1734

页数：4

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