Abstract: Cross-dehydrogenative C–O coupling of N-hydroxyimides with ketones, esters, and carboxylic acids was achieved employing the di-tert-butyl peroxide as a source of free radicals and a dehydrogenating agent. The proposed method is experimentally simple and demonstrates the outstanding efficiency for the challenging CH substrates, such as unactivated esters and carboxylic acids. It was shown that N-hydroxyphthalimide drastically affects the oxidative properties of t-BuOOt-Bu by intercepting the t-BuO• radicals with the formation of phthalimide-N-oxyl radicals, a species responsible for both hydrogen atom abstraction from the CH reagent and the selective formation of the C–O coupling product by selective radical cross-recombination. The practical applicability of the developed method was exemplified by the single-stage synthesis of commercial reagent (known as Baran aminating reagent precursor) from isobutyric acid and N-hydroxysuccinimide, whereas in the standard synthetic approach, four stages are necessary.

Cite: Krylov I.B. , Lopat'eva E.R. , Budnikov A.S. , Nikishin G.I. , Terent'ev A.O.
Metal-Free Cross-Dehydrogenative C–O Coupling of Carbonyl Compounds with N-Hydroxyimides: Unexpected Selective Behavior of Highly Reactive Free Radicals at an Elevated Temperature
Journal of Organic Chemistry. 2019. V.85. N4. P.1935-1947. DOI: 10.1021/acs.joc.9b02656 WOS Scopus OpenAlex

Identifiers:

Web of science:	WOS:000516665800016
Scopus:	2-s2.0-85078668603
OpenAlex:	W2997043922

Citing:

DB	Citing
OpenAlex	24
Scopus	24

Altmetrics: