Efficient Synthesis of an Unprecedented Enantiopure Hybrid Scorpionate/Cyclopentadienyl by Diastereoselective Nucleophilic Addition to a Fulvene

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• 作者：Manuel Honrado ; Antonio Otero ; Juan Fern谩ndez-Baeza ; Luis F. S谩nchez-Barba ; Agustı ; ́ ; n Lara-S谩nchez ; Juan Tejeda ; Marı ; ́ ; a P. Carri贸n ; Jaime Martı ; ́ ; nez-Ferrer ; Andr茅s Garc茅s ; Ana M. Rodrı ; ́ ; guez
• 刊名：Organometallics
• 出版年：2013
• 出版时间：June 24, 2013
• 年：2013
• 卷：32
• 期：12
• 页码：3437-3440
• 全文大小：227K
• 年卷期：v.32,no.12(June 24, 2013)
• ISSN：1520-6041

文摘

The 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 魏p>2p>NN-畏p>1p>(蟺)-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 P_i = 0.77.