Combined Photoredox and Carbene Catalysis for the Synthesis of Ketones from Carboxylic Acids.
Combined Photoredox and Carbene Catalysis for the Synthesis of Ketones from Carboxylic Acids.
复制标题
DOI：
10.26434/chemrxiv.11573400.v1
复制
发表时间：
2020-01
影响因子：
--
通讯作者：
Anna V. Bay;Keegan P. Fitzpatrick;Rick C. Betori;K. Scheidt
中科院分区：
文献类型：
--
作者：
Anna V. Bay;Keegan P. Fitzpatrick;Rick C. Betori;K. Scheidt
作为构建复杂有机支架的关键元素，C--C键的形成仍然是有机合成化学领域的一个挑战。单电子化学的最新进展使形成各种C-1，3-C键的新方法成为可能。本文公开了用于由羧酸形成酮的酰基唑鎓的新型单电子还原的开发。使用合并的NHC-光氧化还原催化剂，可以在原位容易地构建酰基唑，然后进行自由基-自由基偶联。该方案在合成中的实用性在各种药物化合物的后期官能化中得到展示。使用手性NHC的初步研究表明，可以实现对映体选择性，展示了该协议的优势，替代方法。.
As a key element in the construction of complex organic scaffolds, the formation of C–C bonds remains a challenge in the field of synthetic organic chemistry. Recent advancements in single-electron chemistry have enabled new methods for the formation of various C–C bonds. Disclosed herein is the development of a novel single-electron reduction of acyl azoliums for the formation of ketones from carboxylic acids. Facile construction of the acyl azolium in situ followed by a radical-radical coupling was made possible using merged NHC-photoredox catalysis. The utility of this protocol in synthesis was showcased in the late-stage functionalization of a variety of pharmaceutical compounds. Preliminary investigations using chiral NHCs demonstrate that enantioselectivity can be achieved, showcasing the advantages of this protocol over alternative methodologies. .