Decarboxylative Allylic Amidation: Methods and Synthetic Applications

该奖项是根据2009年美国复苏和再投资法案（公法111-5）资助的。本项目将继续研究Ir(I)催化的对映选择性脱羧烯丙基酰胺化反应及相应的分子间烯丙基酰胺化反应的进一步发展，重点研究其合成用途和潜力。特别有趣的研究是烯丙基二烯体系的对映选择性（脱羧）烯丙基酰胺化，它可以产生广泛的光学富集的“正交”保护1,2-/1,3-/1,4-二胺/氨基醇，没有一般的合成方法存在。同时还证明了发达的（脱羧）对映选择性烯丙基酰胺化反应，以及对映选择性（脱羧）烯丙基醚化反应、立体选择性分子内酰胺聚合反应和烯烃复分解反应。可以为许多具有重要生物学意义和合成挑战性的化合物的核心结构基序的不对称合成提供非常通用和有效的策略，例如（多羟基化）吡咯烷和哌啶环，（多羟基化）吲哚嘧啶和吡咯烷环，以及氮杂- c -糖苷。有机和大分子化学项目将通过该奖项支持美国德克萨斯大学圣安东尼奥分校化学系教授韩铉洙的研究。韩教授的研究工作围绕着对映选择性（脱羧）烯丙基酰胺化和醚化反应的发展，以形成C-N/O键。考虑到C-N/O键在几乎所有具有重要生物学意义的有机化合物中普遍存在，该项目的成功开发将对制药、生物医学和农业行业的合成产生影响。

This award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5). This project will continue work on the further development of Ir(I)-catalyzed enantioselective decarboxylative allylic amidation reaction and the corresponding intermolecular allylic amidation reaction, with particular emphasis on their synthetic utility and potential. Particularly interesting to study is enantioselective (decarboxylative) allylic amidation of allylic diene systems, which can generate a broad range of optically enriched 'orthogonally' protected 1,2-/1,3-/1,4-diamines/aminoalcohols, for which no general synthetic method exists. Also demonstrated is that the developed (decarboxylative) enantioselective allylic amidation reactions, in conjunction with enantioselective (decarboxylative) allylic etherification, stereoselective intramolecular amidomercuration, and olefin metathesis reactions, can provide extremely general and efficient strategies for the asymmetric synthesis of the core structural motifs of many biologically significant and synthetically challenging compounds such as (polyhydroxylated) pyrrolidine and piperidine rings, (polyhydroxylated) indolizidine and pyrrolizidine rings, and aza-C-glycosides. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Hyunsoo Han of the Department of Chemistry at the University of Texas at San Antonio. Professor Han's research efforts revolve around the development of enantioselective (decarboxylative) allylic amidation and etherification reactions for the formation of C-N/O bonds. Considering the ubiquitous presence of C-N/O bonds in almost all biologically significant organic compounds, successful development of this project will have an impact on synthesis in the pharmaceutical, biomedical, and agricultural industries.