One-Pot Cascade Reactions for the Synthesis of Dinitroalkanes in Aqueous Buffer
One-Pot Cascade Reactions for the Synthesis of Dinitroalkanes in Aqueous Buffer
复制标题
在水缓冲液中合成二硝基烷烃的一锅级联反应
DOI：
10.1039/d2re00403h
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发表时间：
2023
影响因子：
3.9
通讯作者：
Domaille, Dylan W
中科院分区：
文献类型：
--
作者：
Stewart, Kelsey Nicole;Hawkins, Kendyll G;Andersen, Campbell M.;Domaille, Dylan W
由于 1,3-二硝基基序的多功能性，二硝基烷烃是强大的合成结构单元。在这里，我们证明二硝基烷烃可以在磷酸盐缓冲液和氨基酸赖氨酸催化的三步级联反应中从脂肪醛合成。我们进一步表明，该方法可以扩展到有限的醇底物（1-丁醇和1-戊醇），包括生物催化的醇氧化。同时添加所有试剂，从 1-丁醇和硝基甲烷衍生得到的 3-(硝基甲基)己烷的最大产率可达 52%，而错开引入氨基酸催化剂和硝基甲烷底物可将 3-(硝基甲基)己烷的产率提高到 71%，同时正丁醛中间体的消耗接近定量。总而言之，这项工作提出了一种温和的合成方法，耦合多步催化级联来生成 1,3-二硝基烷烃。
Dinitroalkanes are powerful synthetic building blocks because of the versatility of the 1,3-dinitro motif. Here, we show that dinitroalkanes can be synthesized from aliphatic aldehydes in a three-step cascade reaction catalysed by phosphate buffer and the amino acid lysine. We further show that this methodology can be expanded to limited alcohol substrates (1-butanol and 1-pentanol) with the inclusion of a biocatalysed alcohol oxidation. Simultaneous addition of all reagents gives a maximal yield of 52% of 3-(nitromethyl)hexane, derived from 1-butanol and nitromethane, whereas staggering the introduction of the amino acid catalyst and nitromethane substrate boosts the yield to 71% of 3-(nitromethyl)hexane with near-quantitative consumption of the n-butyraldehyde intermediate. Taken together, this work presents a mild synthetic method that couples multi-step catalytic cascades to generate 1,3-dinitroalkanes.