Exploiting the Reactivity of Isocyanide: Coupling Reaction between Isocyanide and Toluene Derivatives Using the Isocyano Group as an N1 Synthon

Abstract

An unusual oxidative coupling reaction of isocyanide and toluene derivatives using tetrabutylammonium iodide (TBAI) as a catalyst is disclosed. The experimental results and mechanistic study show that the isocyano group acts formally as an N1 synthon during the transformation, thus expanding the reactivity profile of isocyanide.

Metal‐Free Catalyst‐Controlled Chemoselective Synthesis of Aryl α‐Ketoesters and Primary α‐Ketoamides from Aryl Acetimidates

“…On the basis of aforementioned results and relevant literature,–,−, a plausible reaction mechanism for this metal‐free direct benzylic oxidation is depicted in Scheme . The present reaction is initiated by the formation of tert ‐butoxyl and /or tert ‐butylhydroperoxide radicals, which generates from the redox catalytic reaction of TBAI and TBHP ( path a) .…”

A convenient synthesis of N-tert-butyl amides by the reaction of di-tert-butyl dicarbonate and nitriles catalyzed by Cu(OTf)2

“…133–134 °C (lit. 27 133–134 °C). 1 H NMR (500 MHz, CDCl 3 ): δ 7.72 (d, J = 7.5 Hz, 2H), 7.47 (t, J = 7.3 Hz, 1H), 7.41 (t, J = 7.5 Hz, 2H), 5.93 (s, 1H), 1.48 (s, 9H); 13 C NMR (126 MHz, CDCl 3 ): δ 166.9, 136.0, 131.0, 128.4, 126.7, 51.6, 28.9.…”

“…111–112 °C (lit. 27 111–112 °C), 1 H NMR (500 MHz, CDCl 3 ): δ 7.56–7.46 (m, 2H), 7.30–7.26 (m, 2H), 5.93 (s, 1H), 2.38 (s, 3H), 1.47 (s, 9H); 13 C NMR (126 MHz, CDCl 3 ): δ 167.1, 138.3, 136.0, 131.7, 128.3, 127.5, 123.6, 51.5, 28.9, 21.3.…”

Iron Catalyzed α-C-H Cyanation of Simple and Complex Tertiary Amines

“…This broad substrate scope is remarkable, as comparable reaction conditions for the α-C-H cyanation of tertiary amines frequently employ peroxide-based oxidants (e.g., t BuOOH). Such oxidants typically lead free radicals as reaction intermediates, [35][36][37] which can attack olefinic, 38 alkyne, 39,40 and heterocyclic 41 substructures of complex amine substrates and are thus fundamentally limited in their scope. The presented work circumvents this issue by designing an Fe-based catalyst system that potentially relies on substrate binding and a radical-rebound mechanism.…”