Metal-metal bonds

The team is developing synthetic strategies based on the use of reagents having Metalloid-Metal or Metal-Metal bonds. Addition reactions of these compounds across C-C multiple bonds enable the simultaneous creation of two new C–Metal and/or C–Metalloid bonds that can react orthogonally in two successive electrophilic substitution reactions, thus offering the possibility of developing so-called “step-economy” approaches. We are looking for systems with ample functional tolerance, based on elements such as Zn, Cu, Si, B or Ge.

Alkyne germylzincation

  • Synthesis of 6-membered germacycles by intramolecular germylzincation of alkynes. Kassamba, S.; Reboli, M.; Perez-Luna, A.; Ferreira, F.; Durandetti, M. Org. Chem. Front. 2023, 10, 3328–3335. https://dx.doi.org/10.1039/D3QO00647F

Alkyne silylzincation

  • Radical Silyl- and Germylzincation of Propargylic Alcohols. de la Vega-Hernández, K.; Isaac, K.; Chemla, F.; Ferreira, F.; Jackowski, O.; Perez-Luna, A. Helv. Chim. Acta 2021, 104, e2100128 ; http://dx.doi.org/10.1002/hlca.202100128.
  • Development of a Radical Silylzincation of (Het)Aryl-Substituted Alkynes and Computational Insights into the Origin of the trans-Stereoselectivity. Romain, E.; Vega-Hernández, K. de la; Guégan, F.; García, J. S.; Fopp, C.; Chemla, F.; Ferreira, F.; Gerard, H.; Jackowski, O.; Halbert, S.; et al. Adv. Synth. Catal. 2021, 363, 2634–2647 ; http://dx.doi.org/https://doi.org/10.1002/adsc.202001566.
  • Stereodivergent Synthesis of β-Heteroatom-Substituted Vinylsilanes by Sequential Silylzincation–Copper(I)-Mediated Electrophilic Substitution. Fopp, C.; Isaac, K.; Romain, E.; Chemla, F.; Ferreira, F.; Jackowski, O.; Oestreich, M.; Perez-Luna, A. Synthesis 2017, 49, 724–735 ; http://dx.doi.org/10.1055/s-0036-1588106.
  • 4-Amino-1-Allenylsilanes from 4-Aminopropargylic Acetates through a Silylzincation/Elimination Sequence. Bochatay, V. N.; Neouchy, Z.; Chemla, F.; Ferreira, F.; Jackowski, O.; Pérez-Luna, A. Synthesis 2016, 48, 3287–3300 ; http://dx.doi.org/10.1055/s-0035-1562429.
  • Stereodivergent Silylzincation of α-Heteroatom-Substituted Alkynes. Fopp, C.; Romain, E.; Isaac, K.; Chemla, F.; Ferreira, F.; Jackowski, O.; Oestreich, M.; Perez-Luna, A. Org. Lett. 2016, 18, 2054–2057 ; http://dx.doi.org/10.1021/acs.orglett.6b00680.
  • 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.

1,2-Rearrangements of acetylenic silylzincates and silylboronates

  • 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.
  • 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.