A Tale of Two Isomers: Enhanced Antiaromaticity/Diradical Character versus Deleterious Ring-Opening of Benzofuran-fused s-Indacenes and Dicyclopenta[b,g]naphthalenes

被引：29

作者：

Barker, Joshua E. ^{[1
,2
]}

Price, Tavis W. ^{[1
,2
]}

Karas, Lucas J. ^{[3
]}

Kishi, Ryohei ^{[4
,5
,6
]}

MacMillan, Samantha N. ^{[7
]}

Zakharov, Lev N. ^{[8
]}

Gomez-Garcia, Carlos J. ^{[9
,10
]}

Wu, Judy, I ^{[3
]}

Nakano, Masayoshi ^{[4
,5
,6
,11
,12
]}

Haley, Michael M. ^{[1
,2
]}

机构：

[1] Univ Oregon, Dept Chem & Biochem, Eugene, OR 97403 USA

[2] Univ Oregon, Mat Sci Inst, Eugene, OR 97403 USA

[3] Univ Houston, Dept Chem, Houston, TX 77204 USA

[4] Osaka Univ, Dept Mat Engn Sci, Grad Sch Engn Sci, Int Adv Res Inst QIQB IARI, Toyonaka, Osaka 5608531, Japan

[5] Osaka Univ, Ctr Quantum Informat & Quantum Biol, Int Adv Res Inst QIQB IARI, Toyonaka, Osaka 5608531, Japan

[6] Osaka Univ, Div Quantum Photochem Engn, Res Ctr Solar Energy Chem RCSEC, Grad Sch Engn Sci, 1-1 Machikaneyama, Toyonaka, Osaka 5600043, Japan

[7] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14853 USA

[8] Univ Oregon, Ctr Adv Mat Characterizat Oregon CAM COR, Eugene, OR 97403 USA

[9] Univ Valencia, Dept Inorgan Chem, Paterna 46980, Spain

[10] Univ Valencia, Inst Ciencia Mol, Paterna 46980, Spain

[11] Osaka Univ, Inst Open & Transdisciplinary Res Initiat ICS OTR, Innovat Catalysis Sci Div, Suita, Osaka 5650871, Japan

[12] Osaka Univ, Ctr Spintron Res Network CSRN, Grad Sch Engn Sci, Toyonaka, Osaka 5608531, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2021年 / 60卷 / 41期

基金：

美国国家科学基金会; 日本学术振兴会;

关键词：

antiaromaticity; diradicaloid; heterocycles; indacene; polycyclic hydrocarbons; CYCLOOCTATETRAENE; SEMICONDUCTORS; STRATEGY;

D O I：

10.1002/anie.202107855

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We examine the effects of fusing two benzofurans to s-indacene (indacenodibenzofurans, IDBFs) and dicyclopenta[b,g]naphthalene (indenoindenodibenzofurans, IIDBFs) to control the strong antiaromaticity and diradical character of these core units. Synthesis via 3-functionalized benzofuran yields syn-IDBF and syn-IIDBF. syn-IDBF possesses a high degree of paratropicity, exceeding that of the parent hydrocarbon, which in turn results in strong diradical character for syn-IIDBF. In the case of the anti-isomers, synthesized via 2-substituted benzofurans, these effects are decreased; however, both derivatives undergo an unexpected ring-opening reaction during the final dearomatization step. All the results are compared to the benzothiophene-fused analogues and show that the increased electronegativity of oxygen in the syn-fused derivatives leads to enhancement of the antiaromatic core causing greater paratropicity. For syn-IIDBF increased diradical character results from rearomati-zation of the core naphthalene unit in order to relieve this paratropicity.

引用

页码：22385 / 22392

页数：8