Radical-polar reactions with alkylzincs

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Alkylzinc derivatives offer an interesting duality, being able to react both as anion (carbanions) and radical source. A special feature about these reagents is that, on the one hand, they oxidize readily in the presence of oxygen to form alkyl radicals and, on the other, they are excellent partners for homolytic substitution with alkyl radicals (zinc radical transfer). This makes them ideal reagents for developing so-called “radical-polar” sequences. These are radical chain processes initiated by the formation of an alkyl radical from an alkyl zinc in the presence of oxygen. The radical thus produced undergoes one or more radical transformations before being reduced in the medium via a homolytic substitution on the zinc atom (SH2) of the organozinc, thus forming a new organozinc species and an alkyl radical that propagates the radical chain. Overall, the in-situ transformation of an alkylzinc into a new, more elaborate organozinc species is obtained, which can then be functionalized by reaction with an electrophile. Our contribution in this field has focused on the implementation of multi-component strategies in which several C-C bonds are formed in a single synthetic sequence.

Alkyne Germylzincation

  • Modular access to substituted germoles by intramolecular germylzincation. Kassamba, S.; Perez-Luna, A.; Ferreira, F.; Durandetti, M. Chem. Commun.2022, 58, 3901–3904 ; http://dx.doi.org/10.1039/D1CC07163G.
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  • Radical Germylzincation of Aryl- and Alkyl-Substituted Internal Alkynes. de la Vega-Hernández, K.; Chemla, F.; Ferreira, F.; Jackowski, O.; Perez-Luna, A. Org. Lett.2021, 23, 4426–4430 ; http://dx.doi.org/10.1021/acs.orglett.1c01367.
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  • Radical Germylzincation of α-Heteroatom-Substituted Alkynes. de la Vega-Hernández, K.; Romain, E.; Coffinet, A.; Bijouard, K.; Gontard, G.; Chemla, F.; Ferreira, F.; Jackowski, O.; Perez-Luna, A. J. Am. Chem. Soc.2018, 140, 17632–17642 ; http://dx.doi.org/10.1021/jacs.8b09851.
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Alkyne Silylzincation

  • Trans-Selective Radical Silylzincation of Ynamides. Romain, E.; Fopp, C.; Chemla, F.; Ferreira, F.; Jackowski, O.; Oestreich, M.; Perez-Luna, A. Angew. Chem. Int. Ed.2014, 53, 11333–11337 ; http://dx.doi.org/10.1002/anie.201407002.
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Addition–aldol Tandem Processes

  • ?-(Aminomethyl)-acrylates as acceptors in radical–polar crossover 1,4-additions of dialkylzincs: insights into enolate formation and trapping. Palillero-Cisneros, A.; Gordillo-Guerra, P. G.; Garcia-Alvarez, F. ; Jackowski, O. ; Ferreira, F. ; Chemla, F. ; Teran, J. L. Beilstein J. Org. Chem. 2023, 19, 1443–1451. https://doi.org/10.3762/bjoc.19.103
  • Asymmetric Tandem Conjugate Addition–Aldol Condensation with N-Acryloyloxazolidines Derived from 2-Phenylglycinol. Zelocualtecatl-Montiel, I.; García-Álvarez, F.; Juárez, J. R.; Orea, L.; Gnecco, D.; Mendoza, A.; Chemla, F.; Ferreira, F.; Jackowski, O.; Aparicio, D. M.; et al. Asian J. Org. Chem.2017, 6, 67–70 ; http://dx.doi.org/10.1002/ajoc.201600501.
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Heterocycles through carbocyclization 

  • Zinc Radical Transfer Based Modular Approach to Enantiopure Alkylidene-β-Prolines from N-(Tert-Butylsulfinyl)- α-(Aminomethyl)acrylates. Beniazza, R.; Romain, E.; Chemla, F.; Ferreira, F.; Jackowski, O.; Perez-Luna, A. Eur. J. Org. Chem.2015, 7661–7665 ; http://dx.doi.org/10.1002/ejoc.201501173.
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  • Radical Zinc-Atom-Transfer-Based Carbozincation of Haloalkynes with Dialkylzincs. Chemla, F.; Dulong, F.; Ferreira, F.; Perez-Luna, A. Beilstein J. Org. Chem.2013, 9, 236–245 ; http://dx.doi.org/10.3762/bjoc.9.28.
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  • Radical Zinc Atom-Transfer Based Multicomponent Approaches to 3 AlkylideneTetrahydrofurans. Chemla, F.; Dulong, F.; Ferreira, F.; Nüllen, M. P.; Pérez-Luna, A. Synthesis2011, 1347–1360. DOI: 10.1002/adsc.201100333
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  • Radical-polar crossover domino reactions involving organozinc reagents and β-(allyloxy)-enoates. Giboulot, S.; Pérez-Luna, A.; Botuha, C.; Ferreira, F.; Chemla, F. Tetrahedron Lett. 2008, 49, 3963–3966. DOI:10.1016/j.tetlet.2008.04.108
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  • Radical-polar crossover domino reaction involving alkynes: A stereoselective zinc atom radical transfer. Pérez-Luna, A.; Botuha, C.; Ferreira, F.; Chemla, F. Chem ; Eur. J.2008, 14, 8784–8788. DOI: 10.1002/chem.200801451
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