Zhao Jiancheng, Pedersen Christian Marcus, Chang Honghong, Hou Xianglin, Wang Yingxiong, Qiao Yan
Shanxi Engineering Research Center of Biorefinery, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan 030001, China.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
iScience. 2023 Jun 1;26(7):106980. doi: 10.1016/j.isci.2023.106980. eCollection 2023 Jul 21.
Herein, we report choline chloride-based deep eutectic solvents (DESs) promoted conversion of -acetyl-d-glucosamine (GlcNAc) into nitrogen-containing compounds, i.e., 3-acetamido-5-(1',2'-dihydroxyethyl) furan (Chromogen III) and 3-acetamido-5-acetylfuran (3A5AF). The binary deep eutectic solvent choline chloride-glycerin (ChCl-Gly), was found to promote the dehydration of GlcNAc to form Chromogen III, which reaches a maximum yield of 31.1%. On the other hand, the ternary deep eutectic solvent, choline chloride-glycerol-B(OH) (ChCl-Gly-B(OH)), promoted the further dehydration of GlcNAc into 3A5AF with a maximum yield of 39.2%. In addition, the reaction intermediate, 2-acetamido-2,3-dideoxy-d--hex-2-enofuranose (Chromogen I), was detected by nuclear magnetic resonance (NMR) techniques when promoted by ChCl-Gly-B(OH). The experimental results of the H NMR chemical shift titration showed ChCl-Gly interactions with α-OH-3 and α-OH-4 of GlcNAc, which is responsible for promoting the dehydration reaction. Meanwhile, the strong interaction between Cl and GlcNAc was demonstrated by Cl NMR.
在此，我们报道了基于氯化胆碱的低共熔溶剂（DESs）促进了 N-乙酰-D-葡萄糖胺（GlcNAc）向含氮化合物的转化，即 3-乙酰氨基-5-(1',2'-二羟乙基)呋喃（色原 III）和 3-乙酰氨基-5-乙酰基呋喃（3A5AF）。发现二元低共熔溶剂氯化胆碱-甘油（ChCl-Gly）促进 GlcNAc 脱水形成色原 III，其最大产率达到 31.1%。另一方面，三元低共熔溶剂氯化胆碱-甘油-B(OH)（ChCl-Gly-B(OH)）促进 GlcNAc 进一步脱水生成 3A5AF，最大产率为 39.2%。此外，当由 ChCl-Gly-B(OH)促进时，通过核磁共振（NMR）技术检测到反应中间体 2-乙酰氨基-2,3-二脱氧-D-赤藓糖-2-烯呋喃糖（色原 I）。1H NMR 化学位移滴定的实验结果表明 ChCl-Gly 与 GlcNAc 的α-OH-3 和α-OH-4 相互作用，这是促进脱水反应的原因。同时，通过 35Cl NMR 证明了 Cl 与 GlcNAc 之间的强相互作用。
