No abstract

H-Phosphinates react with alkenes and alkynes using catalytic manganese(II) acetate. Under stoichiometric conditions with manganeseA C H T U N G T R E N N U N G (III) acetate or with catalytic manganese(II) acetate + excess manganese(II) oxide various reactions like arylation or cyclization through radical oxidative arylation can take place. Whereas the chemistry of manganese is already well developed for the functionalization of H-phosphonates, the present methodology provides an unprecedented access to functionalized phosphinates in acceptable to good yields.

The N-heterocyclic carbene (NHC)-catalyzed umpolung of aldimines for the synthesis of 4-difluoromethylquinoline derivatives is reported. In the presence of NHCs, the intramolecular cyclization of aldimines bearing a moderately electron-poor double bond due to the presence of the -CF group likely proceeds via the intermediacy of the aza-Breslow intermediate. The key to the success of this aza-Stetter type transformation is the NHC generated from the bicyclic triazolium salt using DBU as the base.