Revisiting the Synthesis and Nucleophilic Reactivity of an Anionic Copper Superoxide Complex

被引：30

作者：

Bailey, Wilson D. ^{[1
]}

Gagnon, Nicole L. ^{[2
,3
]}

Elwell, Courtney E. ^{[2
,3
]}

Cramblit, Anna C. ^{[2
,3
]}

Bouchey, Caitlin J. ^{[1
,2
,3
]}

Tolman, William B. ^{[1
,2
,3
]}

机构：

[1] Washington Univ, Dept Chem, One Brookings Dr,Campus Box 1134, St Louis, MO 63130 USA

[2] Univ Minnesota, Dept Chem, 207 Pleasant St SE, Minneapolis, MN 55455 USA

[3] Univ Minnesota, Ctr Met Biocatalysis, 207 Pleasant St SE, Minneapolis, MN 55455 USA

来源：

INORGANIC CHEMISTRY | 2019年 / 58卷 / 08期

关键词：

CRYSTAL;

D O I：

10.1021/acs.inorgchem.9b00090

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The addition of 1 equiv of KO2 and Kryptofix222 (Krypt) in CH3CN to a solution of LCu(CH3CN) EL = N,N'-bis(2,6-diisopropylphenyl)2,6-pyridinecarboxamide] in tetrahydrofuran at -80 degrees C yielded [K(Krypt)][LCuO2], the enhanced stability of which enabled reexamination of its reactivity with 2-phenylpropionaldehyde (2-PPA). Mechanistic and product analysis studies revealed that [K(Krypt)] [LCuO2] 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 KO2 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.

引用

页码：4706 / 4711

页数：6

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