Preparation of Alkyl Indium Reagents by Iodine-Catalyzed Direct Indium Insertion and Their Applications in Cross-Coupling Reactions

Abstract

An efficient method for the synthesis of alkyl indium reagent by means of an iodine-catalyzed direct indium insertion into alkyl iodide in THF is reported. The thus-generated alkyl indium reagents effectively underwent Pd-catalyzed cross-coupling reactions with various aryl halides, exhibiting good compatibility to a variety of sensitive functional groups. By replacing THF with DMA and using 0.75 equiv of iodine, less reactive alkyl bromide could be used as substrate for indium insertion with equal ease.

CF3SO2Na-Mediated Five-Component Carbonylation of Triarylboroxines with TMSCF3 and THF/LiOH/NaI to Give Aroyloxyalkyl Iodides

“…Recently, the ring-opening reactions of cyclic ethers are recognized as one of the important transformations in organic synthesis, since (1) the cyclic ethers can be easily obtained from the biomass-derived levulinic acid and furfural, and (2) they can provide an effective approach to the difunctional intermediates, such as the aroyloxyalkyl iodide. Since the aroyloxyalkyl iodide is a versatile reaction center in many frequently used reactions, including cross-coupling, alkylation, addition, reduction, organometallic transformations, halogen exchange reaction, radical precursors, iodine source, etc. Therefore, their synthesis has attracted much attention in organic synthesis.…”

Silver Iodide‐mediated Insertion of Indium to Synthesize Water‐tolerant Organoindium Reagents and the Application in Cross‐coupling Reactions

“…The following cross‐coupling reaction of the resulting alkyl indium reagents with different kinds of aryl halides under palladium catalysis was also investigated. The reaction produced products in moderate to good yields and is tolerant to a large fraction of sensitive functional groups such as hydroxyl, acetyl, nitro, cyano, ester and aldehyde groups and with broad functional group compatibility [8–10] …”

“…The reaction produced products in moderate to good yields and is tolerant to a large fraction of sensitive functional groups such as hydroxyl, acetyl, nitro, cyano, ester and aldehyde groups and with broad functional group compatibility. [8][9][10]…”

“…Knochel's research provides a feasible scheme for directly obtaining alkyl indium reagents. [5] Next, Thomas Minehan and colleagues reported the direct insertion of metallic indium into aryl iodides to synthesize organoindium reagents, aryl indium reagents and aryl halides provided biaryl compounds in good yields under the catalysis of palladium. [6] The great attraction of this field has allowed the research on organoindium reagents to continue.…”

Nickel-Catalyzed, para-Selective, Radical-Based Alkylation of Aromatic Ketones

“…Only the Nakao group reported a method that ensures the selective alkylation of aromatic ketones at the para -position via cooperative nickel/aluminum catalysis in 2016 (Scheme b). And recently, Zhou and co-workers reported a para -selective alkylation of electron-deficient arenes using alkyl halides as alkyl sources, but only part of the acetophenone substrate reacted which limits the utility of this reaction . Herein, we report a nickel-catalyzed, para -selective, radical-based alkylation of aromatic ketones with a wide variety of substrates and functional group tolerance.…”