期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 21, 期 42, 页码 14812-14822出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201502534
关键词
lithium; metalation; structure elucidation; triazoles; zinc
资金
- UK Engineering and Physical Science Research Council [EP/K001183/1]
- Royal Society
- Royal Society of Edinburgh (BP Trust Fellowship)
- NSERC Canada
- EPSRC [EP/K001183/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/K001183/1] Funding Source: researchfish
Organometallic bases are becoming increasingly complex, because mixing components can lead to bases superior to single-component bases. To better understand this superiority, it is useful to study metalated intermediate structures prior to quenching. This study is on 1-phenyl-1H-benzotriazole, which was previously deprotonated by an in situ ZnCl2 center dot TMEDA/LiTMP (TMEDA=N,N,N',N'-tetramethylethylenediamine; TMP=2,2,6,6-tetramethylpiperidide) mixture and then iodinated. Herein, reaction with LiTMP exposes the deficiency of the single-component base as the crystalline product obtained was [{4-R-1-(2-lithiophenyl)-1H-benzotriazole center dot 3THF}(2)], [R=2-C6H4(Ph)NLi], in which ring opening of benzotriazole and N-2 extrusion had occurred. Supporting lithiation by adding iBu(2)Al(TMP) induces trans-metal trapping, in which C-Li bonds transform into C-Al bonds to stabilise the metalated intermediate. X-ray diffraction studies revealed homodimeric [(4-R'-1-phenyl-1H-benzotriazole)(2)], [R'=(iBu)(2)Al(mu-TMP) Li], and its heterodimeric isomer [(4-R'-1-phenyl-1H-benzotriazole){2-R'-1-phenyl-1H-benzotriazole}], whose structure and slow conformational dynamics were probed by solution NMR spectroscopy.
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