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. 2014 Apr 9;136(14):5279-82.
doi: 10.1021/ja501879c. Epub 2014 Mar 31.

A mild, ferrocene-catalyzed C-H imidation of (hetero)arenes

Klement Foo  1 , Eran Sella, Isabelle Thomé, Martin D Eastgate, Phil S Baran
Affiliations

A mild, ferrocene-catalyzed C-H imidation of (hetero)arenes

Klement Foo et al. J Am Chem Soc. .

Abstract

A simple method for direct C-H imidation is reported using a new perester-based self-immolating reagent and a base-metal catalyst. The succinimide products obtained can be easily deprotected in situ (if desired) to reveal the corresponding anilines directly. The scope of the reaction is broad, the conditions are extremely mild, and the reaction is tolerant of oxidizable and acid-labile functionality, multiple heteroatoms, and aryl iodides. Mechanistic studies indicate that ferrocene (Cp2Fe) plays the role of an electron shuttle in the decomposition of the perester reagent, delivering a succinimidyl radical ready to add to an aromatic system.

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Figures

Figure 1
Figure 1
(A) Examples of intermolecular oxidative amination of arenes. (B) Preliminary studies toward a radical-based C–H amination reagent. (C) Invention of NSP (7).
Figure 2
Figure 2
(A) Proposed catalytic cycle. (B) Mechanistic probe by 1H NMR spectroscopy.
Scheme 1
Scheme 1. (A) One-Pot C–H Imidation/Deprotection of 4d and 4j and (B) Gram-Scale C–H Imidation of 4d
See this image and copyright information in PMC

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