Active Trans-Membrane Transport through Transition Metal Catalysed Iterative C-H Functionalisation (May Change)

自主的化学燃料定向运动支撑着许多自然界宏伟的生物马达蛋白的功能。在人造小分子系统中模仿或复制这种行为是一个非常令人兴奋的挑战。已经开发了许多人工系统，其允许分子货物跨脂质双层的被动运输。1然而，表现出主动运输的系统开发得不太好。该项目的目的是使用最近开发的新方法，涉及迭代功能化的疏水分子轨道，以创建一个系统，能够积极运输分子货物跨越protocell membranes.By利用文献中报道的两个过程，它已经有可能实现铑催化迭代C-H功能化的联苯，三联苯，硼酸轨道。该方法首次将过渡金属催化的定向基团辅助的C-H官能化与[1，n]过渡金属迁移相结合。找到一种有效合成更长聚苯硼酸轨道的方法将是该项目的关键起点。研究和优化铑催化的迭代C-H官能化这些较长的轨道将遵循。该项目还将涉及新的过渡金属催化迭代功能化方法的开发。利用Gobbo小组在合成原始细胞开发和研究方面的广泛专业知识，我们提出可以将疏水分子轨道插入原始细胞膜，以实现化学燃料条件下分子货物的主动运输。在生物系统中，跨膜转运通常是复杂化学级联或信号传导途径中的关键步骤。在这个项目中，这种复杂的化学网络将被用作开发具有过渡金属催化剂介导的化学信号传导特性的新型合成细胞的灵感。Chen，Y. Wang，T. Nie，C.鲍角，澳-地Wang，T.徐，智-地Lin，L. H. Qu，X.贡，Y.扬湖，澳-地Zhu和H. Tian，J. Am.化学会，2018，140，17992-17998.2）M. Lautens，W. Klute，W.塔姆湖F. Tietze，A. Padwa，M. D. Weingarten，D. F.哈维，D. M.西加诺湾Malacria、E.根岸角科佩雷角妈，S Y. Liou，F. Liu，T. Satoh，Y. Kawamura，M. Miura，M. Nomura，M.卡特拉尼湖Ferioli，F.库吉尼湾波切利河C. Larock和P.L.约翰逊，安吉。化学成分：Int. Ed. Engl，1996，96，42. 3)S.妈妈和Z古安琪Chemie Int. Ed.，2005，44，7512-7517中描述的。

Autonomous chemically-fuelled directional motion underpins the function of many of nature's magnificent biological motor proteins. Mimicking or replicating such behaviour in artificial small molecule systems is a hugely exciting challenge. Numerous artificial systems have been developed which allow the passive transport of molecular cargo across lipid bilayers.1 However, systems which exhibit active transport are much less well developed. The aim of this project is to use a recently developed novel methodology, involving iterative functionalisation of hydrophobic molecular tracks to create a system capable of actively transporting molecular cargo across a protocell membrane.By exploiting two processes reported in the literature, it has been possible to achieve rhodium catalysed iterative C-H functionalisation of biphenyl, and terphenyl, boronic acid tracks. This process combines-for the first time-transition metal-catalysed directing group-assisted C-H functionalisation with [1,n] transition metal migrations. Finding a methodology to efficiently synthesise longer polyphenyl boronic acid tracks will be a key starting point for this project. Investigation and optimisation of the rhodium catalysed iterative C-H functionalisation of these longer tracks will follow. This project will also involve the development of new transition-metal catalysed iterative functionalisation methodologies.Exploiting the Gobbo group's extensive expertise in the development and investigation of synthetic protocells, we propose that the hydrophobic molecular tracks could be inserted across a protocell membrane to achieve active transport of molecular cargo under chemically-fuelled conditions.In biological systems, transport across membranes often represents a crucial step in complex chemical cascades or signalling pathways. In this project, such sophisticated chemical networks will be used as inspiration for the development of novel synthetic cells with transition metal catalyst-mediated chemical signalling properties.1) S. Chen, Y. Wang, T. Nie, C. Bao, C. Wang, T. Xu, Q. Lin, D. H. Qu, X. Gong, Y. Yang, L. Zhu and H. Tian, J. Am. Chem. Soc., 2018, 140, 17992-17998.2) M. Lautens, W. Klute, W. Tam, L. F. Tietze, A. Padwa, M. D. Weingarten, D. F. Harvey, D. M. Sigano, M. Malacria, E. Negishi, C. Copéret, S. Ma, S.-Y. Liou, F. Liu, T. Satoh, Y. Kawamura, M. Miura, M. Nomura, M. Catellani, L. Ferioli, F. Cugini, G. J. Bocelli, R. C. Larock and P. L. Johnson, Angew. Chem., Int. Ed. Engl, 1996, 96, 42. 3) S. Ma and Z. Gu, Angew. Chemie Int. Ed., 2005, 44, 7512-7517.