重新审视阴离子铜超氧化物配合物的合成及亲核反应活性
Revisiting the Synthesis and Nucleophilic Reactivity of an Anionic Copper Superoxide Complex.
作者信息
Bailey Wilson D, Gagnon Nicole L, Elwell Courtney E, Cramblitt Anna C, Bouchey Caitlin J, Tolman William B
机构信息
Department of Chemistry , Washington University-St. Louis , One Brookings Drive, Campus Box 1134 , St. Louis , Missouri 63130-4899 , United States.
Department of Chemistry and Center for Metals in Biocatalysis , University of Minnesota , 207 Pleasant Street SE , Minneapolis , Minnesota 55455 , United States.
出版信息
Inorg Chem. 2019 Apr 15;58(8):4706-4711. doi: 10.1021/acs.inorgchem.9b00090. Epub 2019 Mar 22.
Abstract
The addition of 1 equiv of KO and Kryptofix222 (Krypt) in CHCN to a solution of LCu(CHCN) [L = N, N'-bis(2,6-diisopropylphenyl)-2,6-pyridinecarboxamide] in tetrahydrofuran at -80 °C yielded [K(Krypt)][LCuO], the enhanced stability of which enabled reexamination of its reactivity with 2-phenylpropionaldehyde (2-PPA). Mechanistic and product analysis studies revealed that [K(Krypt)][LCuO] reacts with wet 2-PPA to form [LCuOH], which then deprotonates 2-PPA to yield the copper(II) enolate complex [LCu(OC═C(Me)Ph)]. Acetophenone was observed upon workup of this complex or mixtures of KO and 2-PPA alone, in support of an alternative mechanism(s) to the one proposed previously involving an initial nucleophilic attack at the carbonyl group of 2-PPA.
摘要
在-80℃下，将1当量的KO和穴状配体222（Krypt）加入到四氢呋喃中的LCu(CHCN) [L = N, N'-双(2,6-二异丙基苯基)-2,6-吡啶甲酰胺]溶液中，得到[K(Krypt)][LCuO]，其增强的稳定性使得能够重新研究它与2-苯基丙醛（2-PPA）的反应活性。机理和产物分析研究表明，[K(Krypt)][LCuO]与湿的2-PPA反应形成[LCuOH]，然后[LCuOH]使2-PPA去质子化，生成铜（II）烯醇盐配合物[LCu(OC═C(Me)Ph)]。单独处理该配合物或KO与2-PPA的混合物时会观察到苯乙酮，这支持了一种不同于先前提出的涉及对2-PPA羰基进行初始亲核攻击的替代机理。
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