10.1002/chem.201804504
Chemistry - A European Journal
COMMUNICATION
under reported conditions[23] underwent dihalogenation followed
by amination at the more activated benzylic position to
diastereomerically pure piperidine 10 (Scheme 5). Importantly,
N-methyl sulfamates 11a-d could be applied for amidyl radical-
promoted sequential di- and tribromination within a Hofmann-
Löffler pathway. These reactions again rely on their common
1,6-HAT,[10] and provide selective dibromination for symmetric
11a and for terpene derivative 11b. For the latter, the remote
tertiary C-H bond remains intact due to the absence of any free
radical pathway. The reaction is not restricted to tertiary C-H
bonds, and provides exclusive double bromination at the
benzylic and tertiary positions of 11c, respectively. Furthermore,
in the presence of an excess of hydantoin 2b, multiple
bromination of 11d accesses tribrominated 12d with a geminal
dibromination motif.
Catalonia and to COST Action CA15106 “C
Organic Synthesis (CHAOS)”.
–H Activation in
Keywords: Bromine • C-H Functionalization • Hofmann-Löffler
Reaction • Iodine • Polyhalogenation
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Scheme 5. Multiple halogenation of acyclic apliphatic C-H bonds. [a] With 4
equiv. 2b.
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Acknowledgements
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Financial support was provided by the Spanish Ministry for
Economy and Competitiveness and FEDER (CTQ2017-88496R
grant to K. M., and Severo Ochoa Excellence Accreditation
2014-2018 to ICIQ, SEV-2013-0319). H. Z. thanks ICIQ-
COFUND Program for a postdoctoral fellowship. The authors
are grateful to the CERCA Program of the Government of
[13] X-ray crystallographic data for compounds 3a-c, 3f, 3g, 3k-m, 6b, 6f
and 10 have been deposited with the Cambridge Crystallographic Data
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