Selective Functionalization of Aliphatic Amines via Myoglobin-Catalyzed Carbene N–H Insertion
Selective Functionalization of Aliphatic Amines via Myoglobin-Catalyzed Carbene N–H Insertion
复制标题
通过肌红蛋白催化的卡宾 N-H 插入选择性官能化脂肪胺
DOI：
10.1055/s-0039-1690007
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发表时间：
2020
期刊：
影响因子：
2
通讯作者：
Fasan, Rudi
中科院分区：
文献类型：
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作者：
Steck, Viktoria;Sreenilayam, Gopeekrishnan;Fasan, Rudi
最近，工程肌红蛋白因其催化各种非生物卡宾转移反应的能力而受到关注，包括通过卡宾插入N-H键对胺的官能化。然而，在这种转化的背景下，肌红蛋白和其他基于血球蛋白的生物催化剂的范围在很大程度上局限于作为胺底物的苯胺衍生物和作为卡宾供体的重氮乙酸乙酯。在这份报告中，我们描述了一种基于肌红蛋白的工程催化剂的开发，该催化剂可用于在广泛的取代苯甲胺和α-重氮乙酸酯上促进卡宾N-H插入反应，具有高效率(82-99%的转化率)、高的催化转化率(高达7,000)和对所需的单一插入产物的良好的化学选择性(高达99%)。这种转化的范围可以扩大到环状脂肪胺。这些研究扩展了可用于选择性形成C-N键的生物催化工具箱，C-N键普遍存在于许多天然和合成的生物活性化合物中。
Engineered myoglobins have recently gained attention for their ability to catalyze a variety of abiological carbene transfer reactions including the functionalization of amines via carbene insertion into N–H bonds. However, the scope of myoglobin and other hemoprotein-based biocatalysts in the context of this transformation has been largely limited to aniline derivatives as the amine substrates and ethyl diazoacetate as the carbene donor reagent. In this report, we describe the development of an engineered myoglobin-based catalyst that is useful for promoting carbene N–H insertion reactions across a broad range of substituted benzylamines and α-diazo acetates with high efficiency (82–99% conversion), elevated catalytic turnovers (up to 7,000), and excellent chemoselectivity for the desired single insertion product (up to 99%). The scope of this transformation could be extended to cyclic aliphatic amines. These studies expand the biocatalytic toolbox available for the selective formation of C–N bonds, which are ubiquitous in many natural and synthetic bioactive compounds.
DOI：
10.1039/c4cc08753d
发表时间：
2015-01-28
期刊：
Chemical communications (Cambridge, England)
影响因子：
--
作者：
Sreenilayam G;Fasan R
通讯作者：
Fasan R