The Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain.
J Am Chem Soc. 2011 Jul 20;133(28):10999-1005. doi: 10.1021/ja2042035. Epub 2011 Jun 23.
Rational catalysis design on the basis of a detailed mechanistic understanding has been used to successfully develop the first efficient general Pd-catalyzed aromatic cyanation reaction under the highly sought after practicable conditions: (i) MCN (M = Na or K) as a cyanide source; (ii) low-boiling recyclable solvents; and (iii) minimal quantities of inexpensive, nontoxic promoters. The developed catalytic reaction converts aromatic bromides to the corresponding nitriles in 88-99% isolated yield with NaCN and 0.5-1.0 mol % of a t-Bu(3)P-monoligated Pd catalyst in MeCN-THF within 2 h at 70 °C. The process exhibits high functional group tolerance.
在详细的机理理解的基础上进行合理的催化设计，已经成功地开发出了第一个在高期望的实用条件下高效的通用 Pd 催化芳香族氰化反应：(i) MCN（M = Na 或 K）作为氰源；(ii) 低沸点可回收溶剂；和 (iii) 少量廉价、无毒的促进剂。所开发的催化反应在 70°C 下，在 MeCN-THF 中，用 NaCN 和 0.5-1.0 mol%的 t-Bu(3)P 单配位 Pd 催化剂，在 2 小时内将芳基溴转化为相应的腈，收率为 88-99%。该过程具有高的官能团容忍度。
