Singlet Oxygen for Use in Organic Synthesis

用于有机合成的单线态氧

• 批准号: 180486347
• 负责人: Professor Dr. Axel G. Griesbeck
• 金额: --
• 依托单位: Institut für Organische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2010
• 资助国家: 德国
• 起止时间: 2009-12-31 至 2012-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/180486347?language=en
• 关键词: Singlet; Oxygen; Use; Organic; Synthesis

The central topic of this project is the investigation of singlet oxygen chemistry and its application for the synthesis of polyoxyfunctionalized products. Combining singlet oxygen reactions and subsequent oxygen transfer reactions leads to highly functionalized products with stereochemical information which slem from the initial photooxygenation step. There are four major areas which should be investigated: A) synthesis with 1O2, B) secondary oxygen transfer, C) 1O2 tandem reactions, D) 1O2endoperoxide transformation. In part A, stereoselective synthetic applications of singlet oxygen reactions are to be investigated with emphasis on stereocontrol by hydrogen-bonding and by organocatalytic methods; in part B, products (allylic hydroperoxides and endoperoxides, respectively) that are generated by singlet oxygen reactions are investigated with respect to secondary reductive or oxygen-transfer steps; in part C, tandem processes (1O2/1O2) are developed and investigated in order to find efficient ways to polyoxyfunctionalizations of organic substrates; in part D, possible enantioselective transformations of endoperoxides will be investigated.

本计画的中心议题为单线态氧化学及其在多氧官能化产物合成中的应用。结合单线态氧反应和随后的氧转移反应，导致高度官能化的产品与立体化学信息，从最初的光氧合步骤。有四个主要领域需要研究：A）1 O2合成，B）二次氧转移，C）1 O2串联反应，D）1 O2内过氧化物转化。在A部分中，单线态氧反应的立体选择性合成应用将被研究，重点是通过氢键和有机催化方法的立体控制;在B部分中，产物（烯丙基氢过氧化物和内过氧化物）是由单线态氧反应产生的，相对于二次还原或氧转移步骤进行了研究;在C部分，串联过程（1 O2/1 O2）的开发和研究，以找到有效的方法，有机底物的聚氧官能化;在D部分，可能的内过氧化物的对映选择性转化将进行研究。

项目成果

A new directing mode for singlet oxygen ene reactions: the vinylogous gem effect enables a 1O2 domino ene/[4 + 2] process.

单线态氧烯反应的新导向模式：插烯宝石效应实现1O2多米诺烯/[4 2]过程

• DOI: 10.1021/ol4009602
• 发表时间: 2013
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: Axel G. Griesbeck;Alan de Kiff
• 通讯作者: Alan de Kiff

Functionalized polar 1,2,4-trioxanes as building blocks by singlet oxygenation of 4-hydroxy tiglic acid using the solvent deuterium isotope trick

• DOI: 10.1039/c3ra40555a
• 发表时间: 2013-01-01
• 期刊: RSC ADVANCES
• 影响因子: 3.9
• 作者: Griesbeck, Axel G.;Schlundt, Viktor;Neudoerfl, Joerg M.
• 通讯作者: Neudoerfl, Joerg M.

Comparison of the singlet oxygen ene reactions of cyclic versus acyclic β,γ-unsaturated ketones: an experimental and computational study

• DOI: 10.1016/j.tetlet.2013.03.099
• 发表时间: 2013-06-05
• 期刊: TETRAHEDRON LETTERS
• 影响因子: 1.8
• 作者: Griesbeck, Axel G.;Goldfuss, Bernd;de Kiff, Alan
• 通讯作者: de Kiff, Alan