Development of Dual Transition Metal Activation for Methane and Carbon Dioxide and further Processing to Carbamate Formation

甲烷和二氧化碳的双过渡金属活化及进一步加工形成氨基甲酸酯的开发

• 批准号: 68851173
• 负责人: Professorin Dr. Barbara Kirchner
• 金额: --
• 依托单位: Institut Català dInvestigació Quimica (ICIQ)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2008
• 资助国家: 德国
• 起止时间: 2007-12-31 至 2011-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/68851173?language=en
• 关键词: Development; Dual; Transition; Metal; Activation

Methane and carbondioxide represent two compounds, which are characterised by their relative inertness to transition metal activation. However, under certain reaction conditions, transformation within the coordination sphere of molecular catalysts can be accomplished. We here propose a novel, economic catalytic synthesis of carbamate fine chemicals from the common bulk materials methane, carbondioxide and amines. The carbamate products represent important and versatile nitrogen sources as applied in organic synthesis for pharmaceutical, medicinal and biological research. Accomplishment of the proposed work should therefore have an impact on various European areas of industrial and academic research. The overall reaction foresees an activation reaction of methane within a transition metal complex, followed by amine coordination and carbondioxide insertion reaction. The carbamate product will be generated by a novel reductive elimination, essentially without any side-product formation. The overall sequence will hence constitute an advantageous process in comparison to the currently employed procedure, which involves phosgene and alcohols.Key issues refer to the development of high selectivity for all steps. This can only be accomplished through appropriately tuning the reactivity of the transition metal centre in combination with a suitable ligand scaffold. The advantage of the presented approach lies in an expected relative ease of independent synthesis for all individual compounds. Hence, it should be possible to optimise each of the individual steps both by theory and by experiment in a complementary fashion. The two groups will then jointly arrive at the establishment of a catalytic cycle for this new transformation.

甲烷和二氧化碳代表两种化合物，其特征在于它们对过渡金属活化的相对惰性。然而，在某些反应条件下，可以在分子催化剂的配位范围内完成转化。本文提出了一种以甲烷、二氧化碳和胺为原料，催化合成氨基甲酸酯精细化学品的新方法。氨基甲酸酯产品代表了重要的和多用途的氮源，应用于制药，医学和生物研究的有机合成。因此，拟议工作的完成应该对欧洲工业和学术研究的各个领域产生影响。整个反应预见了甲烷在过渡金属络合物内的活化反应，随后是胺配位和二氧化碳插入反应。氨基甲酸酯产物将通过新的还原消除产生，基本上没有任何副产物形成。因此，与目前使用的涉及光气和醇的方法相比，整个顺序将构成一种有利的方法。关键问题是开发所有步骤的高选择性。这只能通过适当地调节过渡金属中心与合适的配体骨架组合的反应性来实现。所提出的方法的优点在于预期的相对容易的独立合成的所有个别化合物。因此，应该可以通过理论和实验以互补的方式优化每个单独的步骤。然后，这两个小组将共同为这一新的转变建立一个催化循环。