Cyclic reaction networks for new synthetic methodologies.

循环反应网络，其中相反的，但非微观逆反应同时操作，已被柯林斯集团认为是潜在的重要发展新的合成方法。我们希望开发一种基于过渡金属催化原理的新型循环反应网络。C-H氘化的轻度催化方法引起了相当大的兴趣，最近在氘化的小有机分子中发现了作为活性药物的潜力目前的金属催化方法通常需要酸性或强迫条件；通过利用循环反应网络，我们将开发一种新的氘化方法，该方法与当前的催化氘化方法在正交条件下运行同样，轴向手性的重要性也越来越明显，在生物活性分子和不对称催化的手性配体中发现了轴向手性。许多轴手性联芳基分子的氨选择性合成方法已被报道，然而，其中一种尚未开发的方法是联芳基轴的去消旋我们相信我们提出的循环反应网络将允许构型稳定的三取代双芳基通过动态动力学不对称转化和手性转移与手性配体到双芳基轴前所未有的去消旋。参考文献：1)陈晓明，陈晓明，陈晓明，等。中华医学杂志，2019,32 (2):551 - 557；(2)马绍文，陈志强，陈志强，陈志强。Yu Angew。化学。Int。编辑。2014,53,734；3)。郑国强，郑绍华。李世生，叶磊，陈斌。[j] .生物医学工程学报，2012,21 (4):4805

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