Synthesis of Amides by Mild Palladium-Catalyzed Aminocarbonylation of Arylsilanes with Amines Enabled by Copper(II) Fluoride

Abstract

A general Pd-catalyzed synthesis of amides by oxidative aminocarbonylation of arylsilanes under mild conditions was accomplished for the first time. The reaction is promoted by a commercially available copper­(II) fluoride, which acts as a dual silane activator and mild oxidant, enabling highly efficient aminocarbonylation of versatile arylsilanes at atmospheric CO pressure. The reaction is tolerant of a wide range of arylsilanes and various sensitive halide functional groups as well as a broad scope of amines are compatible with this oxidative process using cheap CO. A significant aspect involves the increased efficiency by the catalyst system. The reaction represents a segue into the powerful Pd-catalyzed oxidative transformations of organosilanes.

Visible-Light-Enabled Aminocarbonylation of Unactivated Alkyl Iodides with Stoichiometric Carbon Monoxide for Application on Late-Stage Carbon Isotope Labeling

“…8 However, most methods are only applicable with aryl or vinyl halides and triflate substrates for carbon labeling. 9,10 Most procedures describing the use of alkyl halides typically use an excess of CO. 11 While unlabeled CO is an inexpensive gas, 14 CO is expensive and thus preferably used as a limiting reagent. Substoichiometric 11 CO carbonylation was achieved by Chow et al 12 applicability of the AIBN-catalyzed method on a wide range of functional groups and compatibility with 11 CO (short-lived isotope of carbon), AIBN presents major drawbacks due to its safety profile and toxic nature.…”

“…Carbonylation with carbon monoxide (CO) is a valuable technique for late-stage incorporation of carbon isotopes as it typically displays excellent functional group tolerance and can be applied to join two advanced intermediates. , Classical carbonylation methods utilize transition metal catalysis (i.e., Pd) to incorporate CO into complex drug-like molecules to afford ketones, carboxylic acids, esters, and amides . However, most methods are only applicable with aryl or vinyl halides and triflate substrates for carbon labeling. , Most procedures describing the use of alkyl halides typically use an excess of CO . While unlabeled CO is an inexpensive gas, 14 CO is expensive and thus preferably used as a limiting reagent.…”

Deoxyfluorination with CuF2: Enabled by Using a Lewis Base Activating Group

“…[8] However, there are limited examples of other TM salts in fluorination processes, [9,10] where they are more commonly employed as bases. [11] Here we show the development of a simple method for deoxyfluorination with typically unreactive TM fluorides, using CuF 2 as an example (Scheme 1 b).…”

A new outlook in oxidative transformations and coupling reactions via in situ generation of organic chloramines

“…An efficient method for the synthesis of aryl or arene carboxamides, benzotriazoles, and related compounds from readily available halides is called aminocarbonylation. [ 101–104 ] Metal‐catalyzed aminocarbonylation reaction with N–Cl compound has emerged as a considerable and standard approach for the introduction of amide functionality in chemical synthesis and has significant applications in organic synthesis. Herein, we have selected some prime literature reports that serve this purpose.…”