Department Chemie und Zentralinstitut für Katalyseforschung, Technische Universität München, Lichtenbergstr. 4, 85748, Garching b. München, Germany.
JSB Gymnasium, 91575, Windsbach, Germany.
Chemistry. 2020 Jan 2;26(1):176-180. doi: 10.1002/chem.201904545. Epub 2019 Nov 26.
The generation of arylzinc reagents (ArZnX) by direct insertion of zinc into the C-X bond of ArX electrophiles has typically been restricted to iodides and bromides. The insertions of zinc dust into the C-O bonds of various aryl sulfonates (tosylates, mesylates, triflates, sulfamates), or into the C-X bonds of other moderate electrophiles (X=Cl, SMe) are catalyzed by a simple NiCl -1,4-diazadiene catalyst system, in which 1,4-diazadiene (DAD) stands for diacetyl diimines, phenanthroline, bipyridine and related ligands. Catalytic zincation in DMF or NMP solution at room temperature now provides arylzinc sulfonates, which undergo typical catalytic cross-coupling or electrophilic substitution reactions.
通过直接将锌插入 ArX 亲电试剂的 C-X 键，生成芳基锌试剂（ArZnX）通常仅限于碘化物和溴化物。锌粉插入各种芳基磺酸盐（对甲苯磺酸盐、甲磺酸盐、三氟甲磺酸盐、磺胺酸盐）的 C-O 键，或插入其他中等亲电试剂（X=Cl、SMe）的 C-X 键，在简单的 NiCl-1,4-二氮杂二烯催化剂体系的催化下进行，其中 1,4-二氮杂二烯（DAD）代表二乙酰基二亚胺、菲咯啉、联吡啶和相关配体。在室温下的 DMF 或 NMP 溶液中进行催化锌化反应，现在可以得到芳基磺酸盐，这些磺酸盐可以进行典型的催化交叉偶联或亲电取代反应。
