基于心环烯的碳纳米锥和氮杂碳纳米锥的设计与合成

Carbon nanocones (CNCs) have attracted extensive attention of chemical and material scientists due to its unique structure and properties, as well as their potential application in organic optoelectronic devices and the synthesis of carbon nanomaterials. However, most of CNCs are acquired through physical approach, whose intrinsic disadvantages such as structure deficiency and complexity, as well as purification difficulties, severely limits their further intensive investigation. This project focuses on the synthesis CNCs with determined structure for the first time. The vertex of CNCs can be regarded as bowl shaped PAHs or π-expended corannulene derivatives——penta-peri-pentabenzocorannulene (p-PBC), which can be used for synthesis of its functional derivatives and π-expended derivatives. In the previous work, we designed p-PBC and its analogues penta-peri-pentabenzoazacorannulene (p-PBAC) as well as their corresponding carbon nanocones, among which p-PBC and p-PBAC were synthesized successfully, verified by MALDI-TOF. In this project, we plan to (1) design and synthesize of stable p-PBC derivatives, such as the corresponding metallocene complexs, substituted derivatives and reduction products H5PBC, then synthesis of π-extended derivatives of H5PBC, which is the carbon nanocones (H5CNCs); (2) design and synthesize of p-PBAC and its functional derivatives as well as aza-carbon nanocones (ACNCs). The synthetic strategy established through this project will provide new starting point for further bottom-up synthesis of more complex CNCs and their derivatives.

碳纳米锥(CNCs)独特的曲面结构和潜在的重要用途引起了广泛兴趣。但目前通过物理方法制得的碳纳米锥存在结构缺陷、产物复杂、无法提纯等缺点，限制了对其结构、性质及应用的深入研究。本项目拟采用化学方法合成结构确定、尺寸单一、无缺陷的五角形碳纳米锥，即先合成其锥顶片段——五迫位五苯并心环烯(p-PBC)，再进一步合成p-PBC功能化衍生物和碳纳米锥。前期工作中，我们设计了p-PBC及其氮杂类似物p-PBAC及它们的π-扩展衍生物碳纳米锥和氮杂碳纳米锥，并初步探索了p-PBC和p-PBAC的合成路线。为此，本项目拟（1）设计合成稳定的p-PBC衍生物如茂金属络合物、取代衍生物或还原产物，进而通过π-扩展合成碳纳米锥；（2）设计合成相应的氮杂类似物及其功能化取代衍生物，通过π-扩展合成更大更复杂的氮杂碳纳米锥。本项目建立的合成策略将为进一步设计合成更大更复杂的碳纳米锥、富勒烯的从头合成提供新的起点。

本项目在前期研究工作的基础上，围绕碗型多环芳烃p-PBC和p-PBAC及其功能化衍生物和p-体系扩大的、更大更复杂的多环芳烃，即相应碳纳米锥的合成，研究它们的结构和物理化学性质。着重进行的具体研究内容如下：① 设计合成了结构新颖的碗型多环芳烃p-PBC，我们从简单易得的原料出发，经过两步合成关环前体1,3-二-(2-氯苯基)-2-(2,6-二氯苯基)环戊二烯并[l]菲-1-醇，并成功获得其单晶数据，再经过钯催化的分子内芳香Heck偶联反应，脱去四分子氯化氢，合成了五迫位五苯并心环烯醇p-PBC-OH；将关环前体中的醇羟基进行还原之后，再经过分子内芳香Heck偶联反应即可得到五迫位五苯并心环烯p-PBC。② 设计合成稳定的五迫位五苯并心环烯的官能团化取代衍生物p-PBC-R。③ 利用中心环环戊二烯骨架，通过五迫位五苯并心环烯与过渡金属配合直接合成茂金属衍生物，得到稳定的茂金属化合物p-PBC-[M]。④ 设计合成了碗型多环芳烃氮杂五迫位五苯并心环烯p-PBAC，我们在尝试了多条合成路线之后，发展了一种合成p-PBAC的新方法。⑤ 设计合成了基于p-PBAC的p扩展衍生物——氮杂碳纳米锥。由p-PBAC出发，以硼化-偶联作为关键合成步骤，合成出关环前体，继而用Scholl反应关环。⑥ 建立了一种合成二苯并磺内酰胺类化合物的新方法，该方法以过渡金属钯作为催化剂，在氟化物存在下，通过N-烷氧基苯磺酰胺类化合物和芳炔前体之间发生基于N-烷氧基苯磺酰胺中-SO2NHOMe邻位C-H键官能团化的环化反应，高效、简便地合成出一系列二芳并磺内酰胺类化合物。⑦ 我们以亚砜亚胺作为导向基团，过渡金属钯作为催化剂，建立了一种简单、高效的合成1,2-苯并噻嗪类化合物的新方法。以S-甲基-S-苯基亚砜亚胺作为反应底物，氟化物的存在下， 在导向基团作用下通过C-H键官能团化与芳炔前体发生环化反应，合成了一系列1,2-苯并噻嗪类化合物。