Allenylmetals

Allenyl-propargyl metals are a family of multifunctional reagents that offer a wide range of synthetic possibilities. The preparation of these compounds and the study of their reactivity is one of the team’s reference areas of research. Our work has focused on chiral allenylsilanes and the condensation of allenylzincs or allenylcoppers with tert-butanesulfinylimines. This combination has proved to be a very fruitful marriage, enabling us to develop numerous applications in total synthesis.

  • Stereoselective Synthesis of 4-Hydroxy-1-Silyl-1-Allenylboranes and Access to 2-Silylethynyl-1,3-Diols. El Haj Brahim, I.; Ishak Dridi, I.; Abderrahim, R.; Fabrice Chemla, F.; Ferreira, F.; Jackowski, O.; Pérez-LunaA.;  Asian J. Org. Chem2024, e202400042, accepted; https://doi.org/10.1002/ajoc.202400042
  • β‐Amino Propargylic Fluorides through Stereoselective Electrophilic Fluorodesilylation of 4‐Amino‐1‐allenylsilanes. Bochatay, V. N.; Chemla, F.; Ferreira, F.; Jackowski, O.; Pérez-Luna, A. Eur. J. Org. Chem. 2018, 3862 ; http://dx.doi.org/10.1002/ejoc.201800862.
  • Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides and acetylenic aziridines. Bochatay, V. N.; Debien, L.; Chemla, F.; Ferreira, F.; Jackowski, O.; Perez-Luna, A. C. R. Chim. 2017, 20, 609–616 ; http://dx.doi.org/10.1016/j.crci.2017.02.001.
  • Ring-Opening of N-Tert-Butanesulfinylethynylaziridines with Lithium Tris(dimethylphenylsilyl)zincate: Stereoselective Access to 4-Amino-1-Allenylsilanes. Bochatay, V. N.; Sanogo, Y.; Chemla, F.; Ferreira, F.; Jackowski, O.; Pérez-Luna, A. Adv. Synth. Catal. 2015, 357, 2809–2814 ; http://dx.doi.org/10.1002/adsc.201500347.
  • Three-Carbon Homologation of Diorganozincs with Lithiated Acetylenic Epoxides. Denichoux, A.; Debien, L.; Cyklinsky, M.; Kaci, M.; Chemla, F.; Ferreira, F.; Perez-Luna, A. J. Org. Chem. 2013, 78, 134–145 ; http://dx.doi.org/10.1021/jo302128n.
  • Metallotropic Equilibrium and Configurational Stability of 3-Chloro-1-(Trimethylsilyl)propargyl and -Allenyl Metals: Comparative Study among Lithium, Titanium, and Zinc. Bejjani, J.; Botuha, C.; Chemla, F.; Ferreira, F.; Magnus, S.; Pérez-Luna, A. Organometallics 2012, 31, 4876–4885 ; http://dx.doi.org/10.1021/om300420q.
  • Stereoselective Synthesis of syn-β-Amino Propargylic Ethers. Application to the Asymmetric Syntheses of (+)-ß-Conhydrine and (–)-Balanol. Louvel, J.; Chemla, F.; Demont, E.; Ferreira, F.; Pérez-Luna, A.; Voituriez, A. Adv. Synth. Cat. 2011, 353, 2137–2151. DOI: 10.1002/adsc.201100333
  • Diastereoselective Synthesis of Homopropargylic N-tert-Butylsulfinylamines. Cyclinsky, M.; Botuha, C.; Chemla, F.; Ferreira, F.; Pérez-Luna, A. Synlett 2011, 2681–2684. DOI:10.1021/ol202747p
  • Synthesis of of (–)-Swainsonine and (–)-8-epi-Swainsonine by the Addition of Allenylmetals to Chiral α,ß-Alkoxy Sulfinylimines. Louvel, J.; Chemla, F.; Demont, E.; Ferreira, F.; Pérez-Luna, A. Org. Lett. 2011, 13, 6452–6455. DOI: 10.1021/ol202747p
  • Asymmetric total synthesis of (+)-6-epi-castanospermine through stereoselective formation of a syn,anti acetylenic 2-amino-1,3-diol stereotriad. Louvel, J.; Botuha, C.; Chemla, F.; Ferreira, F.; Pérez-Luna, A.; Demont, E. Eur. J. Org. Chem. 2010, 2921–2926. DOI: 10.1002/ejoc.201000202
  • Stereo- and Enantioselective Synthesis of Acetylenic 2-Amino-1,3-Diol Stereotriads. Voituriez, A.; Pérez-Luna, A.; Ferreira, F.; Botuha C.; Chemla, F. Org. Lett. 2009, 11, 931–934. DOI: 10.1021/ol802912f
  • Expeditious Synthesis of a Common Intermediate of L-1-Deoxyallonojirimycin and L-1-Deoxymannojirimycin. Ferreira, F.; Botuha C.; Chemla, F.; Pérez-Luna, A. J. Org. Chem. 2009, 74, 2238–2241. DOI: 10.1021/jo802757f
  • Concise Synthesis of (2S,3R)-3-Hydroxy-2-phenylpipezridine: An Advanced Key Intermediate of Human Non-Peptide NK-1 Receptor Antagonists. Hélal, B.; Ferreira, F.; Botuha C.; Chemla, F.; Pérez-Luna, A. Synlett 2009, 3115–3118. DOI: 10.1055/s-0029-1218308
  • High-Yielding Synthesis of Sphingoid-Type Bases. Séguin, C.; Ferreira, F.; Botuha C.; Chemla, F.; Pérez-Luna, A. J. Org. Chem. 2009, 74, 6986–6992. DOI: 10.1021/jo901567q
  • Addition of a 3-alkoxy allenylzinc to N-acyliminium ions: new entry to propargyl syn-1,2-aminoalcohol units. Roy, B; Pérez-Luna, A.; Ferreira, F.; Botuha, C.; Chemla, F. Tetrahedron Lett. 2008, 49, 1534–1537. DOI:10.1016/j.tetlet.2007.12.102
  • Stereoselective Synthesis of Enantioenriched Acetylenic 1,2-Amino Alcohols. Chemla, F.; Ferreira, F.; Gaucher, X.; Palais, L. Synthesis 2007, 1235–1241. DOI: 10.1055/s-2007-965989
  • Short and Efficient Asymetric Synthesis of (-)-ß-Conhydrine. Voituriez, A.; Ferreira, F.; Chemla, F. J. Org. Chem. 2007, 72, 5358–5361. https://doi.org/10.1021/jo070760t
  • Asymmetric Synthesis of (–)-1-Hydroxyquinolizidinone, a Common Intermediate for the Syntheses of (–)-Homopumiliotoxin 223G and (–)-Epiquinamide. Voituriez, A.; Ferreira, F.; Perez-Luna, A.; Chemla, F. Org. Lett. 2007, 9, 4705–4708. DOI: 10.1021/ol701952y