Selective formation of γ-lactams via C-H amidation enabled by tailored iridium catalysts

Science
Seung Youn HongSukbok Chang

Abstract

Intramolecular insertion of metal nitrenes into carbon-hydrogen bonds to form γ-lactam rings has traditionally been hindered by competing isocyanate formation. We report the application of theory and mechanism studies to optimize a class of pentamethylcyclopentadienyl iridium(III) catalysts for suppression of this competing pathway. Modulation of the stereoelectronic properties of the auxiliary bidentate ligands to be more electron-donating was suggested by density functional theory calculations to lower the C-H insertion barrier favoring the desired reaction. These catalysts transform a wide range of 1,4,2-dioxazol-5-ones, carbonylnitrene precursors easily accessible from carboxylic acids, into the corresponding γ-lactams via sp3 and sp2 C-H amidation with exceptional selectivity. The power of this method was further demonstrated by the successful late-stage functionalization of amino acid derivatives and other bioactive molecules.

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Citations

Sep 27, 2018·Chemistry : a European Journal·Yu-Feng LiangLutz Ackermann
Sep 6, 2018·Chemistry : a European Journal·Takuya ShimbayashiKouichi Ohe
Nov 27, 2018·Angewandte Chemie·Zijun ZhouEric Meggers
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Aug 9, 2020·Angewandte Chemie·Meredith A AllenAndré M Beauchemin
Mar 30, 2021·Journal of the American Chemical Society·Jeonghyo LeeSukbok Chang
Apr 10, 2021·Journal of the American Chemical Society·Xiang LyuSukbok Chang
Apr 23, 2021·Journal of the American Chemical Society·Euijae LeeSukbok Chang
May 6, 2021·The Journal of Organic Chemistry·Won AnIn Su Kim

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