Department of Chemical Biology , Max-Planck-Institute of Molecular Physiology , Otto-Hahn-Straße 11 , 44227 Dortmund , Germany.
Faculty of Chemistry and Chemical Biology , TU Dortmund , Otto-Hahn-Straße 4a , 44227 Dortmund , Germany.
Org Lett. 2018 Jul 6;20(13):3911-3914. doi: 10.1021/acs.orglett.8b01495. Epub 2018 Jun 14.
A catalytic, metal-free intramolecular rearrangement of benzyl phenyl ethers using nitrosonium salt as a catalyst is described. The optimized reaction conditions enabled a catalytic and metal-free Friedel-Crafts alkylation reaction with benzylic alcohols, producing water as the stoichiometric byproduct. A comprehensive scope (>50 examples) for both approaches and application in drug synthesis were demonstrated. Mechanistic studies suggest a Lewis acid-based mechanism for the metal-free Friedel-Crafts reaction.
描述了一种使用硝𬭩盐作为催化剂的苄基苯醚的催化、无金属的分子内重排。优化的反应条件实现了苄基醇的催化无金属傅克烷基化反应，生成水作为化学计量的副产物。这两种方法具有广泛的应用范围（超过 50 个例子），并在药物合成中得到了应用。机理研究表明，无金属傅克反应的机理基于路易斯酸。
