Gutiérrez Sara, Tomás-Gamasa María, Mascareñas José Luis
Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS), Departamento de Química Orgánica, Universidade de Santiago de Compostela 15705 Santiago de Compostela Spain
Chem Sci. 2022 May 16;13(22):6478-6495. doi: 10.1039/d2sc00721e. eCollection 2022 Jun 7.
Translating the power of transition metal catalysis to the native habitats of enzymes can significantly expand the possibilities of interrogating or manipulating natural biological systems, including living cells and organisms. This is especially relevant for organometallic reactions that have shown great potential in the field of organic synthesis, like the metal-catalyzed transfer of carbenes. While, at first sight, performing metal carbene chemistry in aqueous solvents, and especially in biologically relevant mixtures, does not seem obvious, in recent years there has been a growing number of reports demonstrating the feasibility of the task. Either using small molecule metal catalysts or artificial metalloenzymes, a number of carbene transfer reactions that tolerate aqueous and biorelevant media are being developed. This review intends to summarize the most relevant contributions, and establish the state of the art in this emerging research field.
将过渡金属催化的能力应用于酶的天然环境中,可显著拓展研究或操控包括活细胞和生物体在内的自然生物系统的可能性。这对于在有机合成领域展现出巨大潜力的有机金属反应而言尤为重要,比如金属催化的卡宾转移反应。乍一看,在水性溶剂中,尤其是在与生物相关的混合物中进行金属卡宾化学反应似乎并不容易,但近年来,越来越多的报告证明了这项任务的可行性。无论是使用小分子金属催化剂还是人工金属酶,一系列能够耐受水性和生物相关介质的卡宾转移反应正在被开发出来。本综述旨在总结最相关的研究成果,并确立这一新兴研究领域的现状。