Cyclic reaction networks for new synthetic methodologies.

新合成方法的循环反应网络。

• 批准号: 2625104
• 金额: --
• 依托单位: University of Bristol
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2021
• 资助国家: 英国
• 起止时间: 2021 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2625104
• 关键词: Cyclic; reaction; networks; new; synthetic

Cyclic reaction networks, in which opposing but non-microscopically reverse reactions operate concurrently, have been recognised by the Collins group as of potential importance in the development of novel synthetic methodologies. We are looking to develop a novel cyclic reaction network based on the principles of transition metal catalysis. Mild catalytic methods for C-H deuteration are of considerable interest, with recent potential identified in deuterated small organic molecules as active pharmaceutical agents.1 Current metal-catalysed methods often require acidic or forcing conditions; by harnessing a cyclic reaction network we will develop a novel deuteration methodology that operates under orthogonal conditions to current catalytic deuteration methodologies.2 Similarly, the importance of axial chirality has become increasingly evident, with axial chirality found in bioactive molecules and chiral ligands for asymmetric catalysis. Many methods for atroposelective synthesis of axially chiral biaryl molecules have been reported, however, one such method that has been unexplored is the deracemization of the biaryl axis.3 We believe our proposed cyclic reaction network will allow the unprecedented deracemization of configurationally stable trisubstituted biaryls through a dynamic kinetic asymmetric transformation and the transfer of chirality associated with a chiral ligand to the biaryl axis. Refences: 1) T. Pirali, M. Serafini, S. Cargnin, A. A. Genazzani J. Med. Chem. 2019, 62, 5276; 2) S. Ma, G. Villa, P. S. Thuy-Boun, A. Homs, J.-Q. Yu, Angew. Chem. Int. Ed. 2014, 53, 734; 3) . K. Cheng, S.-H. Xiang, S. Li, L. Ye, B. Tan Chem. Rev. 2021, 121, 4805

柯林斯小组已经认识到循环反应网络在开发新的合成方法中具有潜在的重要性，在循环反应网络中同时进行相反但非微观的逆反应。我们正在寻求开发一种基于过渡金属催化原理的新型环状反应网络。C-H氘化的温和催化方法引起了相当大的兴趣，最近在氘化小有机分子中发现了作为活性药物的潜力。1目前的金属催化方法通常需要酸性或强制条件;通过利用循环反应网络，我们将开发一种新的氘化方法，该方法在与当前催化氘化方法正交的条件下操作。类似地，轴向手性的重要性已经变得越来越明显，在生物活性分子和用于不对称催化的手性配体中发现了轴向手性。已经报道了许多方法用于轴向手性联芳基分子的atroposelective合成，然而，这样的一种方法尚未探索的是联芳基轴的去外消旋化。3我们相信，我们提出的环状反应网络将允许前所未有的去外消旋化的构型稳定的三取代联芳基通过动态动力学不对称转化和转移手性配体相关的手性联芳基轴。参考文献：1）T. Pirali，M. Serafini，S. Cargnin，A. A. Genazzani J. Med. Chem. 2019，62，5276; 2）S.妈，G. Villa，P. S. Thuy-Boun，A. Homs，J. Q.你，安吉。Chem.Int.Ed.2014，53，734; 3）。K.郑，S- H. Xiang，S.利湖，加-地是的，B。Tan Chem. Rev. 2021，121，4805