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Intramolecular Diamination of Alkenes with Palladium(II)/Copper(II) Bromide and IPy 2 BF 4 : The Role of Halogenated Intermediates
Author(s) -
Muñiz Kilian,
Hövelmann Claas H.,
CamposGómez Esther,
Barluenga José,
González José M.,
Streuff Jan,
Nieger Martin
Publication year - 2008
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200700373
Subject(s) - intramolecular force , chemistry , palladium , annulation , bromide , vinyl bromide , catalysis , medicinal chemistry , pyridine , reagent , organic chemistry , combinatorial chemistry
The oxidative intramolecular diamination of alkenes with tethered ureas and related groups as the nitrogen source has been investigated both with the iodonium reagent IPy 2 BF 4 (Py=pyridine) and under palladium catalysis in the presence of copper(II) bromide as a reoxidant. For terminal alkenes, the two procedures enable selective and high‐yielding transformations. Studies with deuterated material led to the conclusion that the reactions proceed through different stereochemical pathways. An advanced protocol for palladium‐catalyzed diamination through six‐membered‐ring annulation was also developed, and the first examples of the intramolecular diamination of internal alkenes are described. In this case, the same stereochemical outcome was observed for the iodonium‐promoted and palladium‐catalyzed transformations. On this basis, it was possible to determine the importance of aminohalogenated intermediates in both diamination reactions. Overall, the disclosed procedures broaden significantly the synthetic applicability of the oxidative intramolecular diamination of alkenes.