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

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

Research output: Contribution to journalArticlepeer-review

Abstract

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(sp3)-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 Ï 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.

Original languageEnglish (US)
Pages (from-to)987-994
Number of pages8
JournalNature Chemistry
Volume7
Issue number12
DOIs
StatePublished - Dec 1 2015

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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