New concepts for the synthesis and reactivity of sulfur ylides
Final Report Abstract
Sulfonium ylides are textbook reagents in organic synthesis. In this project, we have significantly expanded their scope of applications. Thus, we have developed their use for the synthesis of three-membered ring products using an unusual strategy relying on a gold catalyst. The mechanism of these reactions was studied in detail, and hints from those mechanistic studies were then used to develop an enantioselective synthesis of cyclopropanes. That reaction was applied to a very short synthesis of the so-called “cognac lactone” (a compound whose name perfectly reflects its importance to the fragrance and aroma industry). We have also highlighted several other intriguing reactivity aspects of sulfonium ylides, including their first use for an unusual alkene synthesis. https://science.apa.at/site/natur_und_technik/detail.html?key=SCI_20171031_SCI39471352438957982 http://www.chemie.de/news/165511/auch‐in‐der‐chemie‐sind‐aller‐guten‐dinge‐drei.html https://medienportal.univie.ac.at/presse/aktuelle‐pressemeldungen/detailansicht/artikel/auch‐in‐der‐chemie‐sind‐aller‐guten‐dinge‐drei/
Publications
- “Facile carbon-sulfur bond cleavage in diarylsulfonium ylides: a catalytic sulfur-to-silicon group transfer” Chemical Communications 2013, 49, 4292-4294
Xueliang Huang, Richard Goddard and Nuno Maulide
(See online at https://dx.doi.org/10.1039/C2CC35762C) - “Stereoselective Intramolecular Cyclopropanation through Catalytic Olefin Activation” Chemical Science 2013, 4, 1105-1110
Xueliang Huang, Sebastian Klimczyk, Luís F. Veiros and Nuno Maulide
(See online at https://doi.org/10.1039/c2sc21914j) - “Gold-catalysed intermolecular synthesis of alkylidenecyclopropanes through catalytic allene activation” Chemistry – A European Journal 2014, 20, 10636-10639
Juliette Sabbatani, Xueliang Huang, Luís F. Veiros and Nuno Maulide
(See online at https://doi.org/10.1002/chem.201402935) - “Dimeric TADDOL-Phosphoramidites in Asymmetric Catalysis: Domino Deracemization and Cyclopropanation of Sulfonium Ylides” Angewandte Chemie International Edition 2015, 54, 10365-10369. Angewandte Chemie 2015, 127, 10507-10511
Sebastian Klimczyk, Antonio Misale, Xueliang Huang and Nuno Maulide
(See online at https://doi.org/10.1002/ange.201503851) - “Stereoselective Gold(I) Domino Catalysis of Allylic Isomerization and Olefin Cyclopropanation: Mechanistic Studies” The Journal of Organic Chemistry 2015, 80, 5719-5729
Sebastian Klimczyk, Xueliang Huang, Hanspeter Kählig, Luís F. Veiros and Nuno Maulide
(See online at https://doi.org/10.1021/acs.joc.5b00666) - “Synthesis and photocatalytic reactivity of vinylsulfonium ylides” The Journal of Organic Chemistry 2016, 81, 7201–7210
Immo Klose, Antonio Misale and Nuno Maulide
(See online at https://doi.org/10.1021/acs.joc.6b01073) - “A three-membered ring approach to carbonyl olefination” Nature Communications 2017, 8, 1091
Supaporn Niyomchon, Alberto Oppedisano, Paul Aillard and Nuno Maulide
(See online at https://doi.org/10.1038/s41467-017-01036-y) - “(3+2) Cycloadditions of thiouronium ylides: a room temperature, one-pot approach to dihydrothiophenes” The Journal of Organic Chemistry 2018, 83, 2479-2485
James Neuhaus, Péter Angyal, Rik Oost and Nuno Maulide
(See online at https://doi.org/10.1021/acs.joc.7b03255) - “Catalyst-Dependent Selectivity in Sulfonium Ylide Cycloisomerization Reactions” Chemical Science 2018
Rik Oost, James D. Neuhaus, Antonio Misale, Ricardo Meyrelles, Luís F. Veiros and Nuno Maulide
(See online at https://doi.org/10.1039/c8sc02815j)
