高价碘试剂在寡肽、有机氟化物的合成和甲烷氧化中的反应研究

项目名称： 高价碘试剂在寡肽、有机氟化物的合成和甲烷氧化中的反应研究

项目编号： No.21472094

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 张弛

作者单位： 南开大学

项目金额： 90万元

中文摘要： 高价碘试剂是一类容易制备、反应高效且选择性出色、低毒的氧化剂，实验上容易处理，尤其令人感兴趣的是高价碘试剂展现了丰富且独特的化学反应性，可以实现多种类型的化学转化，在天然产物的全合成、新型功能材料等的合成中得到了广泛的应用。本课题组在过去的几年中致力于高价碘化学的研究，发现了若干高价碘试剂的新反应性，例如，首次发现有机三价碘试剂Iodosodilactone可以有效地促进寡肽的合成。我们将继续在高价碘化学领域进行持续的探索，重点是将高价碘试剂特别是课题组自身发展的新试剂和新组合应用到具有重大理论和实际应用意义的有机转化中，具体包括三方面的内容：1) 进行基于高价碘试剂的肽偶联试剂的研究；2) 使用本组开发的新型水溶性五价碘试剂AIBX进行甲烷及其同系物的惰性C-H 键的氧化研究；3) 继续探索高价碘试剂与一个广泛使用的路易斯酸三氟化硼-乙醚络合物的试剂组合在有机氟化物合成中的应用。

中文关键词： 高价碘试剂；反应性；氧化；寡肽；氟化

英文摘要： As a kind of readily available, efficient, highly selective, stable, and environment-friendly oxidant, hypervalent iodine reagents are easily designed to be recyclable ones and are easily handled. In particlar, they have shown versatile reactivities to realize various organic transformations,and are thus applied widely in the total synthesis of natural products and new functional materials. Our group has been dedicated to the research of the chemistry of hypervalent iodine reagents in the past several years, and some new reactivities of different hypervalent iodine reagents have been disclosed in our group.For example, we found that an hypervalent iodine(III) reagent iodosodilactone could efficiently promote the direct condensation between alpha-amino acids to provide oligopeptides without racemization.We will continue conducting research on the new reactivities of various hypervalent iodine reagents, especially focusing on the reactivities having significant theoretical and practical significance induced by the new hypervalent iodine reagents and new combination of them both developed in our group. These include three aspects:1) efficient synthesis of oligopeptides and cyclic peptides using hypervalent iodine reagents as effective coupling reagents, 2) methane and other alkane oxidation with a water soluble hypervalent iodine(V) reagent-AIBX as the terminal oxidant in the Shilov system, 3)fluorination reactions using boron trifluoride etherate as a fluorine source together with a hypervalent iodine reagent.

英文关键词： hypervalent iodine reagents;reactivity;oxidation;oligopeptide;fluorination