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. 2017 Apr 1;8(4):3204-3210.
doi: 10.1039/c7sc00156h. Epub 2017 Feb 24.

Highly chemoselective ruthenium(ii)-catalyzed direct arylation of cyclic and N, N-dialkyl benzamides with aryl silanes

Pradeep Nareddy  1 , Frank Jordan  1 , Michal Szostak  1
Affiliations

Highly chemoselective ruthenium(ii)-catalyzed direct arylation of cyclic and N, N-dialkyl benzamides with aryl silanes

Pradeep Nareddy et al. Chem Sci. .

Abstract

The ruthenium(ii)-catalyzed oxidative cross-coupling of C(sp2)-H bonds with organosilanes has been accomplished for the first time. This novel protocol enlists challenging cyclic and N,N-dialkyl benzamides as weakly-coordinating substrates to achieve highly regioselective C(sp2)-H arylation as a proof-of-concept, taking advantage of the attractive features of organosilanes as coupling partners. This innovative method is characterized by very high chemoselectivity, installing halide functional groups (I, Br, Cl) that are incompatible with Ru(ii)-carboxylate systems employing halides as cross-coupling partners, while obviating the need for sensitive organometallic reagents and cryogenic temperatures typical to the classic directed-ortho-metallation (DoM) techniques, employing benzamides to afford bioactive structural motifs.

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Figures

Fig. 1
Fig. 1. (A) Ruthenium-catalyzed arylation using aryl halides (previous studies), and (B) highly chemoselective Ru(ii)-catalyzed C–H arylation using organosilanes (this study).
Fig. 2
Fig. 2. Examples of biologically-active biaryls bearing tertiary amides.
Scheme 1
Scheme 1. Deuterium incorporation studies.
Scheme 2
Scheme 2. Synthesis of benzylic biaryl amines.
Scheme 3
Scheme 3. Proposed catalytic cycle.
See this image and copyright information in PMC

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