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

通过过渡金属催化的迭代 C-H 功能化进行主动跨膜运输（可能会发生变化）

• 批准号: 2645229
• 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: 2020
• 资助国家: 英国
• 起止时间: 2020 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2645229
• 关键词: Active; Trans; Membrane; Transport; through

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.

自主化学供电的指令运动基于许多大自然宏伟的生物运动蛋白的功能。在人造小分子系统中模仿或复制这种行为是一个令人兴奋的挑战。已经开发了许多人造系统，这些系统允许分子货物在脂质双层群体上被动运输。1然而，暴露于主动运输的系统发育良好。该项目的目的是使用最近开发的新方法，涉及疏水分子轨道的迭代功能化，以创建一个能够在协议膜上主动运输分子货物的系统。通过利用文献中报道的两个过程，可以实现若糖率催化的C-H次酸纤维化型biphenyl，biphenylyl，terecornyl，byphenylyl，terepornyl and trornylyyl，byerphenyl and terphenyl，byphenyl，byphenylyl，byerpor的助教。该过程将第一次转变金属催化的指导C-H功能化与[1，n]过渡金属迁移相结合。找到一种方法来有效合成更长的多苯基硼酸轨道将是该项目的关键起点。这些较长的轨道的研究和优化将随后催化迭代的迭代C-H功能化。该项目还将涉及开发新的过渡金属催化迭代功能化方法。探索Gobbo集团在合成协议的开发和研究方面的广泛专业知识，我们建议可以将疏水性分子轨迹插入跨协议膜上，以实现分子货物的跨度货物的跨度运输。在复杂的化学级联或信号通路中。在这个项目中，这种复杂的化学网络将用作具有过渡金属催化剂介导的化学信号传导特性开发新型合成细胞的灵感。是。化学Soc。，2018，140，17992-17998.2）M。Lautens，W。Klute，W。Tam，L。F. Tietze，A。Padwa，M。D. Weingarten，D。F. F. F. Harvey，D。M. Sigano，M。Malacracia，M。Malacria，M。Malacria，E.Negishi，E.Negishi，C.Copéret，S.Ma，S.Ma，S.-Ma，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和P. L. Johnson，Angew，Angew。 Chem。，Int。 ed。 Engl，1996，96，42。3）S。Ma和Z. Gu，Angew。 Chemie Int。 ed。 ed。，2005，44，7512-7517。