用添加的多环 π 电子系统与形成光响应的 B-P 易斯导体的抗芳香基结构
Naoki Ando1, Takuya Yamada1, Hiroki Narita1
1Department of Chemistry, Graduate School of Science, and Integrated Research Consortium on Chemical Sciences (IRCCS), Nagoya University, Furo, Chikusa, Nagoya 464-8602, Japan.
将环嵌入多环芳中会产生反芳性. 这种新型结构表现出独特的光物理性质和易斯酸度,使-复合物的形成成为可能.
科学领域:
- 有机化学
- 材料科学
- 超分子化学
背景情况:
- 异原子注改变了多环芳的电子特性.
- 兴奋剂将电子接受和易斯酸性特征引入PAH框架.
研究的目的:
- 通过在PAH骨架中嵌入环来合成和表征新型π结合化合物.
- 研究醇部分对PAH电子结构,光物理性质和反应性的影响.
- 探索易斯酸添加物的形成和特性,涉及这些醇嵌入式系统.
主要方法:
- 从特拉利前体合成嵌入的 π 结合化合物.
- 采用了玻化/分子内电友性C-H玻化序列.
- 通过结构分析,光物理测量和X射线结晶学进行表征.
主要成果:
- 合成的平面嵌化合物具有扭曲的中心和柱状的 π 堆叠.
- 一种与烯融合的衍生物显示出强烈的排放和高量子产量,以及显著的易斯酸度.
- 与含的PAH形成一个B-P附带键,该附带键光解离为-PAH.
结论:
- 在PAH中嵌入醇环诱导抗芳香性和独特性质.
- 由此产生的化合物是强大的易斯酸,能够形成稳定的添加物.
- adduct 的光解离会再生出发射性 borole-PAH,表现出动态的超分子行为.
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相关概念视频
Hydroboration-Oxidation of Alkenes
Cycloaddition Reactions: MO Requirements for Photochemical Activation
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Lewis Acids and Bases
