Department of Chemistry, York University, Toronto, ON, Canada.
Angew Chem Int Ed Engl. 2012 Jul 9;51(28):7024-7. doi: 10.1002/anie.201203547. Epub 2012 Jun 8.
Negishi revisited: higher-order alkyl zincates have been subjected to Negishi coupling with alkyl bromides. For the first time, coupling takes place in straight THF, i.e., without a salt additive and a high dielectric co-solvent. This provides evidence that it is the higher-order zincate that undergoes transmetalation to Pd, and not mono-anionic zincates or any of the other species present in the Schlenk equilibrium.
高一级的烷基锌试剂已经与溴代烷烃进行了尼希希偶联反应。这是首次在直链 THF 中进行偶联，即无需盐添加剂和高介电共溶剂。这证明了发生转金属化反应的是高一级的锌试剂，而不是单阴离子锌试剂或 Schlenk 平衡中存在的任何其他物种。
