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Updated: Jul 15, 2026

Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
Dynamic ligand exchange of the lanthanide complex leading to structural and functional transformation: one-pot
Shin-ya Tosaki1, Riichiro Tsuji, Takashi Ohshima
1Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Abstract:
The characteristic property of the lanthanide complex, which easily undergoes a dynamic ligand exchange and alters its structure and function in situ, is described. After the completion of the catalytic asymmetric epoxidation of various alpha,beta-unsaturated amides 2 in the presence of the Sm-(S)-BINOL-Ph3As=O (1:1:1) complex 1 (2-10 mol %), the addition of Me3SiN3 directly to the reaction mixture led to smooth epoxide-opening at room temperature, affording the corresponding anti-beta-azido-alpha-hydroxyamide 4 in excellent overall yield (up to 99%) with complete regioselectivity and excellent enantiomeric excess (up to >99%). The key to the success of the sequential process was the in situ generation of the highly reactive samarium azide complex through dynamic ligand exchange. In situ IR spectroscopy and other experiments provided strong evidence that the samarium azide complex was generated. In addition, the relatively high Lewis basicity of the amide moiety had a key role in the high reactivity of both the epoxidation and the epoxide-opening reactions. Examinations of other nucleophiles such as sulfur or carbon nucleophiles as well as transformations of epoxide-opened products are also described.
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