Chauvier Clément, Finck Lucie, Irran Elisabeth, Oestreich Martin
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623, Berlin, Germany.
Angew Chem Int Ed Engl. 2020 Jul 20;59(30):12337-12341. doi: 10.1002/anie.201916004. Epub 2020 Mar 10.
A method for the catalytic generation of functionalized aryl alkali metals is reported. These highly reactive intermediates are liberated from silyl-protected aryl-substituted diazenes by the action of Lewis basic alkali metal silanolates, resulting in desilylation and loss of N . Catalytic quantities of these Lewis bases initiate the transfer of the aryl nucleophile from the diazene to carbonyl and carboxyl compounds with superb functional-group tolerance. The aryl alkali metal can be decorated with electrophilic substituents such as methoxycarbonyl or cyano as well as halogen groups. The synthesis of a previously unknown cyclophane-like [4]arene macrocycle from a 1,3-bisdiazene combined with a 1,4-dialdehyde underlines the potential of the approach.
报道了一种催化生成官能化芳基碱金属的方法。这些高活性中间体通过路易斯碱金属硅醇盐的作用从硅基保护的芳基取代重氮化合物中释放出来，导致脱硅反应和氮的损失。催化量的这些路易斯碱引发芳基亲核试剂从重氮化合物转移到羰基和羧基化合物上，具有出色的官能团耐受性。芳基碱金属可以用亲电取代基如甲氧基羰基或氰基以及卤素基团进行修饰。由1,3 - 双二氮烯与1,4 - 二醛合成一种前所未知的环芳烷类[4]芳烃大环化合物突出了该方法的潜力。
