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Abstract
Introduction
Protocol
Results
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Chemistry

一个碗烯官能Hexahelicene的铜（Ⅰ）制备催化的非平面多环芳烃单位炔叠氮化物环加成

Published: September 18, 2016
doi:
10.3791/53954
, ,
1GIR MIOMeT, IU CINQUIMA, Área de Química Inorgánica,Universidad de Valladolid

Summary

在这里，我们提出了一个协议，以合成由三个非平面多环芳烃单位复杂的有机化合物，具有合理的收益率容易组装。

Abstract

The main purpose of this video is to show 6 reaction steps of a convergent synthesis and prepare a complex molecule containing up to three nonplanar polyaromatic units, which are two corannulene moieties and a racemic hexahelicene linking them. The compound described in this work is a good host for fullerenes. Several common organic reactions, such as free-radical reactions, C-C coupling or click chemistry, are employed demonstrating the versatility of functionalization that this compound can accept. All of these reactions work for planar aromatic molecules. With subtle modifications, it is possible to achieve similar results for nonplanar polyaromatic compounds.

Introduction

由于其特殊的几何形状，碗烯和helicenes是可以采用远平面的结构并以有趣的性质产生1-15在过去的几年中的分子，搜索分子受体碳纳米管和富勒烯的是一个非常活跃的领域16-19因，主要是，以20-28其潜在的应用作为用于有机太阳能电池，晶体管，传感器和其他装置的材料。在碗烯和富勒烯之间的形状的优良的互补吸引若干研究人员的注意与设计的目标能够通过分散的力量建立的超分子协会的分子受体。29-39

上述非平面多芳化合物的化学是类似于对完全平面分子描述的，但它是有时很难找到合适的条件，以实现期望的选择性和产率。40 </sup>在这项工作中，我们提出通过应用在每一个研究实验室发现很容易和典型的技术具有与良好收益几步3多环芳烃单元的分子（7）的合成。该分子是非常重要的，因为它可以采用一个钳状构象建立与在溶液C 60 37良好的相互作用;并且它可以打开一个研究线作为手性得益于螺烯接头，这是一种手性分子更高的富勒烯的电位受体由于立体异构轴的存在。41-45然而，只有外消旋螺烯将在这项工作中使用。

在这一点上，合成这些受体的唯一限制是helicenes和corannulenes的制备中，因为它们不是可商购的。但是，按照新的方法发表在别处46-48它们可以以合适的量在一段合理的短周期来获得。

Protocol

1.功能化 2,15-Dimethylhexahelicene 2,15-dimethylhexahelicene的Dibromination 称量的过氧化苯甲酰（BPO）（70％的0.356克（1.0毫摩尔）2,15-dimethylhexahelicene的，0.374克（2.1毫摩尔）新鲜重结晶ñ溴代琥珀酰亚胺的（NBS）和24毫克（0.07毫摩尔）（重量）与30％的水作为稳定剂）。将所有的固体在100毫升的Schlenk烧瓶中的磁搅拌棒。由气体抽空的三个周期之后在舒伦克线用惰?…

Representative Results

碗烯（3）和2,15-dimethylhexahelicene（3 b）项可能如下目前的方法46-48以直接的方式具有非常良好的收益率（ 图5）做好准备。两个共享一个公共分子，2,7-二甲基萘，作为起始原料，从而产生发散到最终分子的汇集合成。 <img alt="图5" src="/files/ftp_upload/53954/53…

Discussion

最终化合物7已经经过从非平面多芳前体6的步骤3和3 b相在每个反应中度到非常良好的产率被制备。在这条线路中观察到的主要限制是两个非平面多芳化合物的溴化。然而，在化合物4 中的情况下，自由碗烯的重要量可以回收用于进一步的用途。 4 b的合成是因为我们发现polybromination如?…

Disclosures

The authors have nothing to disclose.

Acknowledgements

This work was funded by the Spanish Ministerio de Economìa y Competitividad (CTQ 2013-41067-P). H.B. acknowledge with thanks a MEC-FPI grant.

Materials

2,15-Dimethylhexahelicene N/A N/A Prepared according to reference 5b,c in the main text.
Corannulene N/A N/A Prepared according to reference 5a in the main text.
N-Bromosuccinimide (NBS) Sigma Aldrich B8.125-5 ReagentPlus®, 99%. Recrystallized from hot water.
Benzoyl peroxide (BPO) Sigma Aldrich B-2030 ~70% (titration). 30% water as stabilizer.
Sodium azide Sigma Aldrich S2002 ReagentPlus®, ≥99.5%.
Gold (III) chloride Hydrate Sigma Aldrich 50778 puriss. p.a., ACS reagent, ≥49% Au basis.
Ethynyltrimethylsilane Sigma Aldrich 218170 98%.
[PdCl2(dppf)] N/A N/A Prepared according to reference 6 in the main text.
CuI N/A N/A Prepared according to reference 7 in the main text.
KF Sigma Aldrich 307599 99%, spray-dried.
(+)-Sodium L-ascorbate Fluka 11140 BioXtra, ≥99.0% (NT).
Copper(II) Sulphate 5-hydrate Panreac 131270 for analysis.
Carbon tetrachloride (CCl4) Fluka 87030 for IR spectroscopy, ≥99.9%.
Dichloromethane (DCM) Fisher Scientific D/1852/25 Analytical reagent grade. Distilled prior to use.
Hexane Fisher Scientific H/0355/25 Analytical reagent grade. Distilled prior to use.
Ethyl acetate Scharlau AC0145025S Reagent grade. Distilled prior to use.
Tetrahydrofuran (THF) Fisher Scientific T/0701/25 Analytical reagent grade. Distilled prior to use.
1,2-Dichloroethane (DCE) Sigma Aldrich D6,156-3 ReagentPlus®, 99%.
Methanol (MeOH) VWR 20847.36 AnalaR NORMAPUR.
Triethyl amine (NEt3) Sigma Aldrich T0886 ≥99%.
Silica gel Acros 360050010 Particle size 40-60mm.
Sand – low iron Fisher Scientific S/0360/63 General purpose grade.
TLC Silica gel 60 F254 Merck 1.05554.0001
Monowave 300 (Microwave reactor) Anton Para
Sonicator Grupo Selecta 3000513 6 Litres.
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Tags

CorannuleneHexaheliceneCopper(I)-catalyzed Alkyne-azide CycloadditionNonplanar Polyaromatic UnitsClick ChemistryRadical ReactionsCarbon-carbon CouplingDebrominationColumn Chromatography

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Álvarez, C. M., Barbero, H., Ferrero, S. Preparation of a Corannulene-functionalized Hexahelicene by Copper(I)-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units. J. Vis. Exp. (115), e53954, doi:10.3791/53954 (2016).
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