New concepts for the synthesis and reactivity of sulfur ylides

硫叶立德的合成和反应性的新概念

• 批准号: 186516469
• 负责人: Professor Dr. Nuno Maulide
• 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 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/186516469?language=en
• 关键词: New; concepts; synthesis; reactivity; sulfur

Sulfur ylides occupy a very important place as classical textbook reagents in organic chemistry. Recently, we have developed a robust concept for the direct synthesis of sulfonium ylides by a one-step ylide transfer that proceeds in high levels of efficiency. We have also discovered a novel reactivity manifold of sulfonium ylides towards gold catalysts that enables a versatile synthesis of polysubstituted furans and furanones bearing quaternary centers.Herein, we propose an extended array of new methodologies for catalytic transformations of sulfur ylides under mild conditions. An innovative cyclopropanation of electron-neutral olefins, that has the potential to proceed with high levels of asymmetric induction and which shall offeran attractive alternative to current state-of-the-art methods involving explosive and hazardous diazo compounds, will be developed. Improved chemistry for ylide transfer shall render those processes sustainable and cheap. In addition, mechanistic and theoretical studies shall provide key insight on the details of these reactions. Finally, an unprecedented allylic isomerisation of allylic esters, encountered in the course of preliminary studies in this field, willbe studied.

硫叶立德作为有机化学中的经典试剂，在有机化学中占有非常重要的地位。最近，我们已经开发了一个强大的概念，直接合成锍叶立德的一步叶立德转移，收益在高水平的效率。我们还发现了一种新的硫叶立德对金催化剂，使多取代呋喃和呋喃酮轴承quaternarycenters.There，我们提出了一个扩展阵列的新方法，在温和的条件下催化转化硫叶立德的反应性流形。将开发一种创新的电子中性烯烃的环丙烷化反应，该反应具有进行高水平不对称诱导的潜力，并且将为涉及爆炸性和危险的重氮化合物的当前最先进的方法提供极具吸引力的替代方案。改进叶立德转移的化学过程将使这些过程可持续和廉价。此外，机理和理论研究应提供这些反应的细节的关键见解。最后，一个前所未有的烯丙基异构化的烯丙基酯，在这一领域的初步研究过程中遇到的，willbe研究。

项目成果

Synthesis and Photocatalytic Reactivity of Vinylsulfonium Ylides.

• DOI: 10.1021/acs.joc.6b01073
• 发表时间: 2016-07
• 期刊: The Journal of organic chemistry
• 作者: Immo Klose;Antonio Misale;N. Maulide

Dimere TADDOL‐Phosphoramidite in der asymmetrischen Katalyse: Domino‐Deracemisierung/Cyclopropanierung von Sulfoniumyliden

• DOI: 10.1002/ange.201503851
• 发表时间: 2015-08
• 期刊: Angewandte Chemie
• 作者: Sebastian Klimczyk;Antonio Misale;Xueliang Huang;Nuno Maulide

Gold-catalyzed intermolecular synthesis of alkylidenecyclopropanes through catalytic allene activation.

通过催化丙二烯活化金催化分子间合成亚烷基环丙烷

• DOI: 10.1002/chem.201402935
• 发表时间: 2014
• 期刊: Chemistry
• 作者: Juliette Sabbatani;Xueliang Huang;Luís F. Veiros;Nuno Maulide
• 通讯作者: Nuno Maulide

(3+2) Cycloadditions of Thiouronium Ylides: A Room-Temperature, One-Pot Approach to Dihydrothiophenes.

• DOI: 10.1021/acs.joc.7b03255
• 发表时间: 2018-02
• 期刊: The Journal of organic chemistry
• 作者: J. Neuhaus;Péter Angyal;Rik Oost;N. Maulide

Facile carbon-sulfur bond cleavage in diarylsulfonium ylides: a catalytic sulfur-to-silicon group transfer.

• DOI: 10.1039/c2cc35762c
• 发表时间: 2013-04
• 期刊: Chemical communications
• 影响因子: 4.9
• 作者: Xueliang Huang;R. Goddard;N. Maulide