Manganese/bipyridine-catalyzed non-directed C(sp³)–H bromination using NBS and TMSN₃

Abstract

A Mn(II)/bipyridine-catalyzed bromination reaction of unactivated aliphatic C(sp3)−H bonds has been developed using N-bromosuccinimide (NBS) as the brominating reagent. The reaction proceeded in moderate-to-good yield, even on a gram scale. The introduced bromine atom can be converted into fluorine and allyl groups.

Taming Bromine Azide for Use in Organic Solvents─Radical Bromoazidations and Alcohol Oxidations

“…In-situ formation was achieved by OXONE-mediated oxidation of a mixture of sodium bromide and sodium azide and continuously mixing with the organic substrate. Recently, Shi and co-workers disclosed a protocol describing the formation of BrN 3 ( 5 ) from TMSN 3 , N -bromosuccinimide, and iodosobenzene diacetate ( 2 ) used in various radical chemistry applications …”

“…Recently, Shi and co-workers disclosed a protocol describing the formation of BrN 3 ( 5 ) from TMSN 3 , N -bromosuccinimide, and iodosobenzene diacetate ( 2 ) used in various radical chemistry applications. 9 …”

Earth-abundant 3d transition metals on the rise in catalysis

“…In this thematic issue, strategies are presented that guarantee position-selectivity in copper-mediated isoindolin-1-one synthesis [12] as well as in copper-catalyzed aminations of ferrocenes [13]. The exploitation of the innate reactivity of organic molecules can allow for indirected C-H transformations and herein, homolytic C-H cleavages are described for transformative manganese-catalyzed brominations of tertiary C-H bonds [14]. Finally, electrooxidation enabled the site-selective alkynylation of tetrahydroisoquinolines within a TEMPO/copper regime [15].…”