Comer Eamon, Organ Michael G
Department of Chemistry, York University, 4700 Keele Street, Toronto, Ontario, Canada, M3J 1P3.
J Am Chem Soc. 2005 Jun 8;127(22):8160-7. doi: 10.1021/ja0512069.
A capillary-based flow system has been developed for conducting microscale organic synthesis with the aid of microwave irradiation. The capillary internal diameter investigated ranged from 200 to 1200 mum, while the flow rate was varied between 2 and 40 muL/min, which corresponds to the sample being irradiated approximately 4 min. Other parameters investigated include reaction concentration and power setting of the microwave. Excellent conversion was observed in a variety of cross coupling and ring-closing metathesis (RCM) reactions employing metal catalysts and in nucleophilic aromatic substitution and Wittig reactions that do not employ metals. Reactions that have solids in them do not seem to pose a significant concern for the method, such as blocked channels. It was shown that capillaries coated internally with thin films of Pd metal show tremendous rate accelerations and that the thin films themselves are capable of catalyzing Suzuki-Miyaura reactions with no exogenous catalyst added. Importantly, it has been demonstrated that reagents in separate syringes can be coinjected into the capillary, mix, and react with none of the laminar flow problems that plague microreactor (lab on a chip) technology. This paves the way to use microwave-assisted, flow capillary synthesis as a powerful and efficient means to replace "one-at-a-time" microwave synthesis to provide libraries of compounds in a scale suitable for biological screening purposes.
一种基于毛细管的流动系统已被开发出来,用于在微波辐射的辅助下进行微尺度有机合成。所研究的毛细管内径范围为200至1200微米,而流速在2至40微升/分钟之间变化,这相当于样品被辐照约4分钟。所研究的其他参数包括微波的反应浓度和功率设置。在使用金属催化剂的各种交叉偶联和关环复分解(RCM)反应以及不使用金属的亲核芳香取代反应和维蒂希反应中都观察到了优异的转化率。其中含有固体的反应似乎对该方法并不构成重大问题,例如通道堵塞。结果表明,内部涂有钯金属薄膜的毛细管显示出巨大的速率加速,并且这些薄膜本身能够在不添加外源催化剂的情况下催化铃木-宫浦反应。重要的是,已经证明可以将单独注射器中的试剂共注入毛细管中,混合并反应,而不会出现困扰微反应器(芯片实验室)技术的层流问题。这为使用微波辅助的流动毛细管合成作为一种强大而有效的手段来取代“一次一个”的微波合成,以提供适合生物筛选目的规模的化合物库铺平了道路。