‘‘C–H activation is at the center of organic chemistry’’ - Albert Eschenmoser, 2010. C-H bonds are ubiquitous in organic compounds. Novel reactions that can selectively functionalize carbon–hydrogen bonds are of intense interest to the chemical community because they offer new strategic approaches for organic synthesis. Until recently, the majority of metal catalyzed C−H functionalization was achieved employing precious second- and third-row transition metals. Owing to the high reactivity as well as selectivity in the catalytic systems, Cp*Rh(III)-catalysts have captivated immense attraction to the organic chemists. Amide bonds are ubiquitous in a wide range of pharmaceuticals, agrochemicals, and natural products. Atom-economic construction of C–N bonds has been perceived as one of the central topics in organic synthesis. In this context, direct C–H amination of aldehydes C(sp2)–H would be a mild, atom-economic alternative approach. Due to their significant coordinating property and cleavable polar N–O bond, we contemplated that anthranils may serve as substrates in the C–H amination reaction of aldehydes. Particularly, this strategy could provide amide bearing a nucleophilic amino group tethered to an electrophilic carbonyl moiety, which can be difficult to introduce. The amination shows a wide substrates scope, and several important functional groups were tolerated under the benign reaction conditions. The synthesized amides are important precursors for the preparation of benzoxazinone derivatives, found in various bioactive natural products.

Cp*RhIII-catalyzed chelation assisted directed amidation of aldehydes using anthranils

256th National Meeting (2018)

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