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配体诱导的β-二酮亚胺镁配合物通过C-H或C-F键活化实现氟代芳烃区域选择性官能化的反应活性。

Ligand-induced reactivity of β-diketiminate magnesium complexes for regioselective functionalization of fluoroarenes via C-H or C-F bond activations.

作者信息

Davin Laia, McLellan Ross, Kennedy Alan R, Hevia Eva

机构信息

WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK.

出版信息

Chem Commun (Camb). 2017 Oct 24;53(85):11650-11653. doi: 10.1039/c7cc07193k.

Abstract

Using β-diketiminate Mg(ii) complexes containing either alkyl, aryl or amide groups, the regioselective functionalization of a wide range of fluoroarenes is accomplished but in uniquely different ways. Overcoming common limitations of traditional s-block bases, kinetically activated [(Nacnac)Mg(TMP)] (1) deprotonates these molecules at room temperature, trapping sensitive fluoroaryl anions that can then engage in Negishi cross-coupling; whereas [(Nacnac)Mg(R)THF] (R = Bu, Ph, benzofuryl) have proved to be effective reagents for C-F bond alkylation/arylation via pyridine directed C-F bond cleavage.

摘要

使用含有烷基、芳基或酰胺基的β-二酮亚胺镁(II)配合物,可以实现多种氟代芳烃的区域选择性官能化,但方式独特且不同。动力学活化的[(Nacnac)Mg(TMP)](1)克服了传统s区碱的常见局限性,在室温下使这些分子去质子化,捕获敏感的氟代芳基阴离子,然后这些阴离子可参与Negishi交叉偶联;而[(Nacnac)Mg(R)THF](R = Bu、Ph、苯并呋喃基)已被证明是通过吡啶导向的C-F键裂解实现C-F键烷基化/芳基化的有效试剂。

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