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首页> 外文期刊>Chemistry: A European journal >Adding a Structural Context to the Deprotometalation and Trans-Metal Trapping Chemistry of Phenyl-Substituted Benzotriazole
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Adding a Structural Context to the Deprotometalation and Trans-Metal Trapping Chemistry of Phenyl-Substituted Benzotriazole

机译：为苯取代的苯并三唑的原金属化和跨金属捕获化学添加结构背景

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摘要

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.
机译：有机金属碱正变得越来越复杂，因为混合组分可导致优于单组分碱的碱。为了更好地理解这种优势，在淬火之前研究金属化的中间结构非常有用。这项研究是针对1-苯基-1H-苯并三唑，该苯先前已通过原位ZnCl2中心点TMEDA / LiTMP（TMEDA = N，N，N'，N'-四甲基乙二胺; TMP = 2,2,6,6）去质子化-四甲基哌啶）混合物，然后碘化。在此，与LiTMP的反应暴露出单组分碱的不足，因为获得的结晶产物为[{4-R-1-（2-lithiophenyl）-1H-苯并三唑中心点3THF}（2），[R = 2 -C6H4（Ph）NLi]，其中发生了苯并三唑的开环和N-2挤出。通过添加iBu（2）Al（TMP）来支持锂化会引起跨金属陷阱，其中C-Li键转变为C-Al键以稳定金属化的中间体。 X射线衍射研究表明同二聚体[（4-R'-1-苯基-1H-苯并三唑）（2）]，[R'=（iBu）（2）Al（mu-TMP）Li]及其异二聚体异构体[（4-R'-1-苯基-1H-苯并三唑）{2-R'-1-苯基-1H-苯并三唑}]的结构和缓慢的构象动力学通过溶液NMR光谱探测。

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