Carbon-Hydrogen Bond Activation Using Si, Ge, and Sn

这个无机、生物无机和有机金属化学项目的奖项支持密歇根大学Mark M. Banaszak-Holl教授的研究，该研究利用硅烯、二甲苯或锡烯与芳基卤化物一起进行分子间ch活化，并确定这些新反应的机制。这一新知识将应用于将碳氢活化与有机合成领域中重要的反应相结合的过程，例如使用Stille交叉偶联形成碳-碳键。这种化学反应是ch活化化学的第一个例子，它直接导致碳和14族元素之间形成键。这种新的化学反应是由一种鲜为人知的自由基反应引起的，这种反应是由硅烯、硅烯或硅烯与芳基卤化物之间的相互作用引起的，这种反应激活苯基环上的酰基碳来进行氢的提取，同时允许在类金属和活性碳氢化合物的碳之间形成新的键。激活碳氢化合物，然后立即将合成过程进行到下一步的能力，将使一些合成有机反应更容易适应环境。另一个环境效益是，这种化学反应可能有助于使硅基合成试剂更容易获得，从而有助于取代锡的使用。该研究项目还与密歇根化学科学的教育接口（CSIE）和本科生研究经验（REU）项目进行对接，以培训我们的下一代科学家，包括目前在研究生院或担任教职的少数族裔参与者。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Mark M. Banaszak-Holl at the University of Michigan to utilize silylene, germylene or stannylene together with an aryl halide for intermolecular CH-activation and to determine the mechanism of these new reactions. This new knowledge will be applied to processes that combine C-H activation with reactions important in the area of organic synthesis, such as the formation of carbon-carbon bonds using Stille cross-coupling. This chemistry represents the first example of CH-activation chemistry leading directly to the formation of bonds between carbon and group-14 elements. This new chemistry occurs by a poorly understood, radical reaction initiated by the interaction between the silylene, germlene, or silylene and the aryl halide that activates the ipso carbon of the phenyl ring to perform a hydrogen abstraction, while at the same time allowing formation of a new bond between the metalloid and the carbon of the activated hydrocarbon.The ability to activate the hydrocarbon and then immediately carry on the synthetic process to the next step would make some synthetic organic reactions more amenable to the environment. An additional environmental benefit is that this chemistry may help to make silicon-based synthetic reagents more accessible and thus help to replace the use of tin. This research program also interfaces with the Michigan Chemical Sciences at the Interface of Education (CSIE) and Research Experiences for Undergraduates (REU) programs for the training of our next generation of scientists including minority participants who are now in graduate school or hold faculty positions.