Photoredox/Bronsted Acid Co-Catalysis Enabling Decarboxylative Coupling of Amino Acid and Peptide Redox-Active Esters with N-Heteroarenes
Photoredox/Bronsted Acid Co-Catalysis Enabling Decarboxylative Coupling of Amino Acid and Peptide Redox-Active Esters with N-Heteroarenes
复制标题
DOI：
10.1021/acscatal.6b03215
复制
发表时间：
2017-01-01
期刊：
影响因子：
12.9
通讯作者：
Fu, Yao
中科院分区：
文献类型：
--
作者：
Cheng, Wan-Min;Shang, Rui;Fu, Yao
铱光氧化还原催化剂与磷酸结合，在室温下、辐射下催化天然和非天然 α-氨基酸衍生的氧化还原活性酯（N-羟基邻苯二甲酰亚胺酯）的脱羧 α-氨基烷基化，其底物范围广泛为 N-杂芳烃。二肽和三肽衍生的氧化还原活性酯也是适合在肽 C 末端实现 N-杂环脱羧插入的底物，产生具有潜在医学应用的分子。该反应成功的关键因素如下：使用具有合适氧化还原电位的光氧化还原催化剂来可控地产生α-氨基烷基自由基，而不发生过度氧化，以及使用酸性助催化剂来增加N-杂芳烃的电子缺陷。
An iridium photoredox catalyst in combination with a phosphoric acid catalyzes the decarboxylative alpha-aminoalkylation of natural and unnatural alpha-amino acid-derived redox-active esters (N-hydroxyphthalimide esters) with a broad substrate scope of N-heteroarenes at room temperature under irradiation. Dipeptide- and tripeptide-derived redox-active esters are also amenable substrates to achieve decarboxylative insertion of a N-heterocycle at the C-terminal of peptides, yielding molecules that have potential medicinal applications. The key factors for the success of this reaction are the following: use of a photoredox catalyst of suitable redox potential to controllably generate alpha-aminoalkyl radicals, without overoxidation, and an acid cocatalyst to increase the electron deficiency of N-heteroarenes.