Davin Laia, McLellan Ross, Kennedy Alan R, Hevia Eva
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK.
Chem Commun (Camb). 2017 Oct 24;53(85):11650-11653. doi: 10.1039/c7cc07193k.
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.
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。