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

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.

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。

高价碘试剂因其具有反应性丰富、毒性低、易处理、容易获得、稳定性高等优点，是合成化学工作者在有机合成中的常用氧化剂。我们课题组长期致力于高价碘化学的研究，特别是新型有机高价碘试剂的开发和反应性探究。在项目资助期内，我们课题组设计合成了两个新型有机高价碘试剂并揭示了它们在重要的有机转化中的反应性。另外，我们课题组还报道了两个已经存在的高价碘试剂介导的三个新型反应性。具体的研究内容分列如下：1）新型三价碘试剂FPID介导的成肽反应研究；2）水溶性五价碘试剂AIBX的反应性研究；3）新型水溶性三价碘试剂PISA的设计合成及其在吲哚合成中的应用；4）亚碘酰苯类化合物介导的新型反应性研究；5）Koser试剂介导的环状β-二羰基化合物的氧化双脱氢反应研究等。