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Chemo‐ and Stereoselective NBS‐Promoted Intermolecular Oxygenation and Nitrogenation of α‐C–H Bonds of Tertiary Diamines
Author(s) -
Pereira Raul,
Otth Elisabeth,
Cvengroš Ján
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500062
Subject(s) - chemistry , nucleophile , intermolecular force , carbocation , olefin fiber , catalysis , stereoselectivity , medicinal chemistry , oxygen , nitrogen , bicyclic molecule , oxygen atom , organic chemistry , molecule
Abstract A new method for the activation of the non‐benzylic α‐C–H bonds in tertiary diamines has been developed. The protocol relies on an N ‐bromosuccinimide (NBS)‐mediated oxidation of carbon atoms next to the nitrogen atoms in the presence of a catalytic amount of Pd(OAc) 2 followed by an intermolecular reaction with oxygen‐ or nitrogen‐centered nucleophiles. Mechanistic studies hint towards a radical intermediate, which can be further oxidized to an olefin or a non‐classical carbocation. Stable α‐oxygen‐ or α‐nitrogen‐substituted bicyclic tertiary amines are thus efficiently accessed under mild conditions.