Investigation of the remote acyl group participation in glycosylation from conformational perspectives by using trichloroacetimidate as the acetyl surrogate,Organic Chemistry Frontiers

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Investigation of the remote acyl group participation in glycosylation from conformational perspectives by using trichloroacetimidate as the acetyl surrogate
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2020-05-20 , DOI: 10.1039/d0qo00363h
Ke Xu _{1,

2,

3,

4,

5} , Qingmin Man _{5,

6,

7,

8,

9} , Yang Zhang _{1,

2,

3,

4,

5} , Jia Guo _{1,

2,

3,

4,

5} , Yichu Liu _{1,

2,

3,

4,

5} , Zunyun Fu _{5,

8,

9,

10,

11} , Yueyue Zhu _{1,

2,

3,

4,

5} , Yingxia Li _{1,

2,

3,

4,

5} , Mingyue Zheng _{4,

5,

8,

9,

12} , Ning Ding _{1,

2,

3,

4,

5}

Affiliation

Unlike the O2 neighboring group participation in glycosylation, the participating effect of esters located on more remote positions of glycopyranosyl donors has not been unambiguously established and provokes plenty of questions. Here we systematically trapped the participation intermediates on three common pyranoses based on a ‘bis-trichloroacetimidates method’, which showed that trichloroacetimidate group participations from O4 and O6 are all quite possible except for D-mannopyranosyl O4. Besides, with the trapped participation intermediates in hand, the NMR data was collected to assist the DFT calculations to build up the most possible participating conformations, which, in turn, predicted the potentials of remote participation by trichloroacetimidates at different positions on the same donor. Finally, the ‘tris-trichloroacetimidates method’ was employed to support the computational calculations. This work provided a conformational perspective on understanding the potent remote acyl group participation in glycosylation reaction.

中文翻译：

通过构象的角度，通过使用三氯乙酰亚氨酸酯作为乙酰基替代物，研究远端酰基基团参与糖基化的过程

与O 2邻近基团参与糖基化不同，位于糖吡喃糖基供体更远位置的酯的参与作用尚未明确确定，并引发了许多问题。在这里，我们系统地捕获在基于“双trichloroacetimidates方法”，这表明，三氯乙酰亚胺基参股从三种常见吡喃糖参与中间体Ò 4和ö 6都相当可能除了d -mannopyranosyl ö4.此外，利用手中被捕获的参与中间体，收集了NMR数据以协助DFT计算建立最可能的参与构象，从而预测了三氯乙酰亚胺在同一位置上不同位置的远程参与的可能性。捐赠者。最后，采用“三-三氯乙酰亚胺酸酯法”来支持计算。这项工作为理解强力远程酰基参与糖基化反应提供了构象的观点。

更新日期：2020-06-30

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