硫取代分子碗的环重建:一种双[5,6,7]稠和的平面杂环分子的合成
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- 英文论文题名：Ring Reconstruction on a Trichalcogenasumanene Buckybowl:A Approach to Dual-[5-6-7]Fused Planar Polyheterocycles
- 论文作者：侯学清 ; 王世涛 ; 孙彦涛 ; 耿瑞丽 ; 邵向锋
- 英文论文作者：Xueqing Hou ; Shitao Wang ; Yantao Sun ; Ruili Geng ; Xiangfeng Shao ; State Key Laboratory of Applied Organic Chemistry ; University of Lanzhou
- 年：2016
- 作者机构：兰州大学功能有机分子化学国家重点实验室;
- 论文关键词：分子碗 ; 氧化 ; 稠环 ; 结构解析
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第二十一分会：π-共轭材料
- 语种：中文
- 分类号：O626
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：174k
- 原文格式：O
- 会议级别：全国
摘要
富勒烯的发现引发了人们对曲面稠环芳烃化合物(PAHs),即分子碗化合物(Bowl-shaped molecules)的研究兴趣,这些化合物在电学、光学、生物学、磁学和其他领域有着广泛的潜在应用价值。最近,我们利用TPHP为氧化剂,在温和的条件下实现了从硫取代素馨烯(Sumanene)分子碗到一种双[5,6,7]稠和的平面杂环分子的转化,此转化过程包含一种高效氧化两个侧翼苯环开环和功能化环化反应,基于这种开环反应,对其进行进一步功能化衍生,构造了新型的双[5,6,7]稠和的平面杂环化合物。理论计算结果表明:由于侧翼的两个六元环变成了七元环,释放了环张力,使得这种双[5,6,7]稠和的杂环分子具有平面结构;另外,由于给电子的基团的引入,使得这种稠和杂环分子的HOMO-LUMO能带隙降低,同时其紫外吸收带也大幅变宽。
The transformation of trichalcogenasumanene buckybowls into dual-[5,6,7]fused polyheterocycles is disclosed.The strategy involves a double of highly efficient ring-opening of two flanking benzene upon oxidation at facile condition,and facile ring closure by functionalgroup transformation.Theoretical calculation shows that the resulting dual-[5,6,7]fused polyheterocycles possess a planar conformation owing to the release of ring strain by expansion of two of the six-membered flanking rings to the seven-membered one.respectively.Additionally,the dual-[5,6,7]fused polyheterocycles bear electron-withdrawing groups,which reduce the HOMO-LUMO energy gap,and broaden the absorption bands.
The transformation of trichalcogenasumanene buckybowls into dual-[5,6,7]fused polyheterocycles is disclosed.The strategy involves a double of highly efficient ring-opening of two flanking benzene upon oxidation at facile condition,and facile ring closure by functionalgroup transformation.Theoretical calculation shows that the resulting dual-[5,6,7]fused polyheterocycles possess a planar conformation owing to the release of ring strain by expansion of two of the six-membered flanking rings to the seven-membered one.respectively.Additionally,the dual-[5,6,7]fused polyheterocycles bear electron-withdrawing groups,which reduce the HOMO-LUMO energy gap,and broaden the absorption bands.
引文
[1]Li,X.;Zhu,Y;Shao,J.;Wang,B.;Zhang,S.;Shao,Y;Shao,X.*Angew.Chem.Int.Ed,2014,53:535-538.
[2]Li,X.;Zhu,Y;Shao,J.;Chen,L.;Zhao,S.;Shao,Y;Shao,X.*Angew.Chem.Int.Ed.?2015,54:267-271.
[3]Li,X.;Shao,X.*Synlett.,2014,25:1795-1798.
[2]Li,X.;Zhu,Y;Shao,J.;Chen,L.;Zhao,S.;Shao,Y;Shao,X.*Angew.Chem.Int.Ed.?2015,54:267-271.
[3]Li,X.;Shao,X.*Synlett.,2014,25:1795-1798.