Cascade Cope/Winstein Rearrangements: Synthesis of Azido-Cycloheptadienes from Dialkenylcyclopropanes Possessing a Vinyl Azide.

-1,2-Dialkenylcyclopropanes incorporating a vinyl azide, generated by Knoevenagel condensations between the corresponding cyclopropanecarbaldehydes and α-azido ketones, undergo cascade Cope and Winstein [3,3]-sigmatropic rearrangements, under mild conditions. The sequence allows access to diversely substituted 1,4-cycloheptadienes armed with a secondary allylic azide with up to three stereocenters.

Amination of Phosphorodiamidate-Substituted Pyridines and Related N-Heterocycles with Magnesium Amides.

The amination of various phosphorodiamidate-substituted pyridines, quinolines, and quinoxaline with magnesium amides RNMgCl·LiCl proceeds at room temperature within 8 h. Several pharmaceutically active amines were suitable substrates for this amination procedure, and also the antihistaminic tripelennamine was prepared. Additionally, several heterocyclic phosphorodiamidates underwent directed ortho-metalation (D oM) using TMPMgCl·LiCl (TMP = 2,2,6,6-tetramethylpiperidyl) or TMPMg·2LiCl, followed by electrophilic functionalization prior to the amination step, which led to ortho-functionalized aminated N-heterocycles.