Efficient Synthesis of an Unprecedented Enantiopure Hybrid Scorpionate/Cyclopentadienyl by Diastereoselective Nucleophilic Addition to a Fulvene
2013; American Chemical Society; Volume: 32; Issue: 12 Linguagem: Inglês
10.1021/om4003279
ISSN1520-6041
AutoresManuel Honrado, Antonío Otero, Juan Fernández‐Baeza, Luis F. Sánchez‐Barba, Agustín Lara‐Sánchez, Juan Tejeda, María Dolores Pérez‐Carrión, Jaime Martı́nez-Ferrer, Andrés Garcés, Ana M. Rodrı́guez,
Tópico(s)Coordination Chemistry and Organometallics
ResumoThe work described here represents the first example of an enantiopure hybrid scorpionate/cyclopentadiene ligand. The ligand was obtained in a one-pot synthetic procedure by an efficient and highly diastereoselective nucleophilic addition of an organolithium reagent to an electrophilically activated olefin in a new fulvene with a chiral substrate to control the stereochemistry of a newly created asymmetric center. We verified the potential utility of this ligand as a valuable scaffold that is able to induce chirality in organometallic/coordination chemistry. This was achieved through the preparation of a new enantiomerically pure zinc complex in which the ligand behaves in a tridentate manner with a κ2NN-η1(π)-Cp coordination mode. This alkylzinc complex constitutes the first example of an organozinc derivative which behaves as an efficient initiator for the ROP of rac-LA in the production of isotactic-enriched poly(lactides) with Pi = 0.77.
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