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Chemistry
多功能 CO2转化为复杂产品:单罐两步战略
多功能 CO2转化为复杂产品:单罐两步战略
JoVE Journal
Chemistry
This content is Free Access.
JoVE Journal Chemistry
Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

多功能 CO2转化为复杂产品:单罐两步战略

Full Text
8,476 Views
07:36 min
November 9, 2019

DOI: 10.3791/60348-v

Sarah Desmons*1,2, Dan Zhang*1, Angelica Mejia Fajardo1, Sebastien Bontemps1

1LCC-CNRS,Université de Toulouse, CNRS, 2LISBP,Université de Toulouse, CNRS, INRA, INSA

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Please note that some of the translations on this page are AI generated. Click here for the English version.

Overview

This protocol describes a one-pot two-step procedure for the synthesis of complex molecules through CO2 transformations. The method involves the selective 4 e- reduction of CO2 using a hydroborane reductant to generate a reactive bis(boryl)acetal intermediate, which is then utilized in subsequent reactions.

Key Study Components

Area of Science

  • Chemistry
  • Organic Synthesis
  • Carbon Dioxide Utilization

Background

  • CO2 reduction is crucial for synthesizing carbon compounds.
  • The method allows for the generation of versatile intermediates.
  • Visual demonstrations enhance understanding of the complex procedures.
  • Safety precautions are essential due to the handling of gases.

Purpose of Study

  • To control the full electron reduction of CO2.
  • To utilize the generated product as a reactive intermediate.
  • To demonstrate a cascade reaction strategy for compound synthesis.

Methods Used

  • Preparation of reaction mixtures inside a glove box.
  • Pressurization with CO2 and strict temperature control.
  • Sequential addition of reagents and monitoring via NMR analysis.
  • Vacuum removal of volatiles to isolate products.

Main Results

  • Successful generation of bis(boryl)acetal compound.
  • Characterization of compounds through proton NMR analysis.
  • Yield reproducibility confirmed for compound synthesis.
  • Identification of key NMR signals for each compound.

Conclusions

  • The method provides a reliable approach for CO2 transformation.
  • Intermediate reactivity can be effectively probed.
  • Safety measures are critical in handling hazardous materials.

Frequently Asked Questions

What is the significance of CO2 reduction in this study?
CO2 reduction is significant as it allows for the synthesis of valuable carbon compounds from a greenhouse gas.
What precautions should be taken during the experiment?
Precautions include using a glove box for handling sensitive materials and following safety sheets for hazardous gases.
How are the reaction conditions controlled?
Reaction conditions are controlled through precise temperature management and CO2 pressurization.
What techniques are used to analyze the products?
Products are analyzed using proton NMR to confirm their structure and yield.
Can this method be applied to other reactions?
Yes, the cascade strategy can be adapted for various synthetic pathways involving reactive intermediates.

CO2变换在单罐两步过程中进行,用于合成复杂分子。选择性 4 e-使用氢硼还原剂减少 CO2提供了一种反应性和多功能的乙醛中间体,随后参与冷凝反应或碳介C-C耦合生成。

该协议意义重大,因为我们可以控制二氧化碳的全电子还原,并且我们可以在单锅级联反应中将产品形式用作反应性和多功能中间体。得益于关键的CO2减排步骤和级联策略,该技术和中间反应性反向探测导致第一步从CO2中合成碳化合物。反应混合物制备是一个细致的过程,涉及在手套箱内的反应容器中增加多个,CO2 加压,以及严格的时间和温度控制。

这种级联策略需要后续的反应步骤、手套箱的使用和气体处理,所有这些都更容易通过视觉演示理解。对于化合物二的合成,用15.9毫克的9BBN、130微升的10%六甲基苯作为内部标准,以及100微升1%摩尔铁催化剂溶液在脱氢四氢黄素中充电。在关闭管子并将其连接到手套箱外的气体系统之前,向管子中加入0.37毫升额外的四氢化物。

将 NMR 管放在 25 摄氏度的浴缸中 15 分钟。然后加入一个二氧化碳大气三分钟,然后关闭管子,在25摄氏度下孵育45分钟。在平衡期间,通过混合189微升新鲜蒸馏的2、6-二异丙乙胺和811微升新鲜脱白四氢黄素,准备库存溶液。

当化合物一产生时,打开手套箱内的 NMR 管,并在管中加入 55 微升的已准备的 2、6-二异丙乙胺溶液。然后关闭并摇动管子 10 秒钟。20分钟后,通过质子 NMR 分析确认 imine 2 的形成,通过将信号与内部标准进行比较,确定 NMR 产量。

对于化合物三的合成,用9.4毫克铁催化剂、320毫克9-BBN和10毫升四氢黄酮在手套箱内向含有磁性搅拌棒的反应容器充电。关闭反应容器后,将其从手套箱中拆下,以连接到气体系统。向容器中加入一个二氧化碳大气三分钟,然后关闭容器,在摄氏25度下搅拌45分钟。

在反应结束时,打开手套箱中的反应容器,在混合物中加入380毫克三甲醇-5-二苯胺溶液。然后用三个大气中的二氧化碳对反应进行充电,并在60摄氏度下搅拌60分钟。反应结束时,当溶液冷却至室温时,去除真空下的挥发物,并在零摄氏度下用两毫升二乙醚洗涤残留物三次,获得二氧化碳三作为白色粉末。

对于手套箱中的化合物四合成,为含有159毫克9-BBN、10%六甲基苯和4.7毫克铁催化剂的新反应容器充电,然后加入5毫升四氢黄素。将封闭容器放在手套箱外,在 25 摄氏度下平衡 15 分钟,然后将容器连接到气体系统 3 分钟,在一个大气二氧化碳的动态压力下。在加压结束时,在25摄氏度下关闭容器进行45分钟的搅拌孵育。

当化合物一产生时,打开手套箱中的反应容器,并加入54毫克三甲醇-5-二苯乙烯。在手套箱外,在80摄氏度下搅拌溶液40分钟,产生含有化合物四的化合物混合物,并在真空下去除溶剂。然后将部分残留物溶解在0.6毫升脱盐四氢素中,并通过装有0.2微米聚四氟乙烯过滤器的注射器将溶液应变成NR管进行分析。

根据质子 NMR 分析评估,成功生成双(玻利二)乙酰化合物一,结果在去氧化四氢黄中,其典型甲基安非他明峰值为百万分之 5.4。化合物二的成功生成为两种不相义的三氢子胺质子的特征 AB 峰值设定为百万分之 7.30。在成功生成化合物三中,最显著的信号是与碳化物相连的甲苯峰,其含量为百万分之5.34,BBN片段的甲苯峰为0.26,负0.65分为百万分之一。

成功合成由二氧化碳产生的化合物四原位,其特点是伪三胞胎的二氧化碳含量为百万分之四点六四,为百万分之三点三。从DL-甘油醛分离的化合物4的分体C3链在质子核磁共振中以四个质子信号为特征,在碳13 NMR中,以三个碳信号为特征。减少步骤对协议的变化很敏感,必须特别通过化合物二的生殖合成来探究可重复性。

请务必检查安全表,了解是否有危险材料和气体,以在气体处理时采取预防措施,并避免造成过压。

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