Details

Autor(en) / Beteiligte

• Paradine, Shauna M
• Griffin, Jennifer R
• Zhao, Jinpeng
• Petronico, Aaron L
• Miller, Shannon M
• Christina White, M

Titel

A manganese catalyst for highly reactive yet chemoselective intramolecular C(sp(3))-H amination

Ist Teil von

• Nature chemistry, 2015-12, Vol.7 (12), p.987-994

Ort / Verlag

England

Erscheinungsjahr

2015

Quelle

MEDLINE

Beschreibungen/Notizen

• C-H bond oxidation reactions underscore the existing paradigm wherein high reactivity and high selectivity are inversely correlated. The development of catalysts capable of oxidizing strong aliphatic C(sp(3))-H bonds while displaying chemoselectivity (that is, tolerance of more oxidizable functionality) remains an unsolved problem. Here, we describe a catalyst, manganese tert-butylphthalocyanine [Mn((t)BuPc)], that is an outlier to the reactivity-selectivity paradigm. It is unique in its capacity to functionalize all types of C(sp(3))-H bond intramolecularly, while displaying excellent chemoselectivity in the presence of π functionality. Mechanistic studies indicate that [Mn((t)BuPc)] transfers bound nitrenes to C(sp(3))-H bonds via a pathway that lies between concerted C-H insertion, observed with reactive noble metals such as rhodium, and stepwise radical C-H abstraction/rebound, as observed with chemoselective base metals such as iron. Rather than achieving a blending of effects, [Mn((t)BuPc)] aminates even 1° aliphatic and propargylic C-H bonds, demonstrating reactivity and selectivity unusual for previously known catalysts.