Alkyl Indium Reagents Research Articles

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

AbstractA direct synthesis method of efficient and mild water‐resistant organoindium reagents and their cross‐coupling reactions with aryl iodide by palladium‐catalyzed was described. At room temperature, organic indium reagents were mediated by AgI, and water‐tolerant alkyl indium reagents were directly and efficiently synthesized. The cross‐coupling reaction of organic indium reagents with various aryl halides could perform smoothly with palladium catalysis. The expected products were obtained in moderate to good yields, and the best yield can reach 99 %. These reactions are promising for their high reactivity, broad applicability, and functional group tolerance.

Palladium-catalyzed cross-coupling of alkylindium reagent with diaryliodonium salt

The palladium-catalyzed cross-couplings of alkylindium reagents with diaryliodonium salts proceeded efficiently in the presence of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4], 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), lithium tert-butoxide, and lithium chloride in DMA/THF (1:1) at 100 °C, leading to the corresponding cross-coupling products in moderate to good yield with broad substrate scope and wide functional group tolerance.

Cobalt(II)-catalyzed preparation of alkylindium reagents and applications in cross-coupling with aryl halides

The direct insertion of indium powder into alkyl iodides was found to be efficiently catalyzed by a catalytic amount of cobalt(II) bromide (10 mol%). Upon subjection of the thus-formed alkylindium compounds to palladium-catalyzed cross-coupling reactions with a wide range of aryl halides, a series of cross-coupled products could be obtained in moderate to good yields with the tolerance to many important functional groups.

Cesium carbonate‐catalyzed indium insertion into alkyl iodides and their synthetic utilities in cross‐coupling reactions

A catalytic amount of cesium carbonate (10 mol%) was found to be capable of effectively catalyzing the insertion of indium powder into alkyl iodides. The thus‐generated alkyl indium reagents could readily undergo palladium‐catalyzed cross‐coupling reactions with a wide variety of aryl halides, showing compatibility to a range of important functional groups.

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

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.

Metallic salt-catalyzed direct indium insertion into alkyl iodides and their applications in cross-coupling reactions

An efficient method for the synthesis of alkyl indium reagents via an indium(iii) or lead(ii) halide-catalyzed direct insertion of indium into alkyl iodides is developed. NMR and ESI-MS analyses indicated the formation of a mixture of an alkyl indium dihalide (RInX2) and a dialkyl indium halide (R2InX).

Palladium-Catalyzed Cross-Coupling of Alkylindium Reagents

Palladium-Catalyzed Cross-Coupling of Alkylindium Reagents

Synthesis of Alkyl Indium Reagents by Using Unactivated Alkyl Chlorides and Their Applications in Palladium-Catalyzed Cross-Coupling Reactions with Aryl Halides.

An efficient method for the preparation of alkyl indium reagents by using unactivated and cheap alkyl chlorides as substrates in the presence of indium and LiI was developed. The thus-formed alkyl indium species effectively underwent palladium-catalyzed cross-coupling reactions with aryl halides with wide functional group tolerance.

In situ generation of phosphoryl alkylindiums and their synthetic application to arylalkyl phosphonates via palladium-catalyzed cross-coupling reactions.

Phosphoryl alkylindium reagents are generated in situ from the direct insertion of indium with bromoalkyl phosphonates in the presence of CuCl, and their synthetic application to arylalkyl phosphonates is reported via a Pd-catalyzed cross-coupling reaction with tolerance of a diversity of functional groups including ester, ketone, aldehyde, nitrile, nitro, trifluoromethyl, chloride, methoxy, hydroxy, and amino.

Organocatalytic SOMO reactions of copper(I)-acetylide and alkylindium compounds with aldehydes

AbstractThe derivatisation of aldehydes in their α-position is an important facet of organic synthesis. Organocatalytic radical reactions afford α-functionalised aldehydes via a SOMO activation pathway. New organo-SOMO reactions of aldehydes with copper(I)-acetylide and alkylindium reagents are detailed. These reactions proceed well under the catalysis of chiral imidazolidinones. The corresponding functionalised aldehydes were obtained with acceptable yields, but with only low enantiomeric ratios.

ChemInform Abstract: Direct Synthesis of Water‐Tolerant Alkyl Indium Reagents and Their Application in Palladium‐Catalyzed Couplings with Aryl Halides.

AbstractAlkyl indium compounds are prepared through a CuCl‐mediated direct insertion of indium into alkyl iodides or bromides under an air atmosphere and even in the presence of water.

Direct Synthesis of Water‐Tolerant Alkyl Indium Reagents and Their Application in Palladium‐Catalyzed Couplings with Aryl Halides

A direct result: Alkyl indium reagents are synthesized by the insertion of indium into alkyl halide mediated by CuCl. The synthetic utility of these reagents is demonstrated by their palladium-catalyzed coupling with aryl halides (see scheme). The reagents are compatible with various functional groups, and this makes the protocol generally useful in organic synthesis. DMA=N,N-dimethylacetamide, TBS=tert-butyldimethylsilyl.

Direct Synthesis of Water-Tolerant Alkyl Indium Reagents and Their Application in Palladium-Catalyzed Couplings with Aryl Halides

Direct Synthesis of Water-Tolerant Alkyl Indium Reagents and Their Application in Palladium-Catalyzed Couplings with Aryl Halides

Highly Selective Palladium‐Catalyzed Oxidative Csp2Csp3 Cross‐Coupling of Arylzinc and Alkylindium Reagents through Double Transmetallation

Abstractmagnified imageUsing desyl chloride (2‐chloro‐1,2‐diphenylethanone) as the oxidant, the palladium‐catalyzed reaction of arylzinc with alkylindium reagents occurred smoothly in a highly selective manner to afford the products in 57–90% yields. Preliminary kinetic data indicated that alkylindium reagents were highly favored for transmetallation with the alkoxy‐palladium moiety.

Palladium-Catalyzed Oxidative Carbonylation of Alkyl and Aryl Indium Reagents with CO under Mild Conditions

CO now can react with organoindium reagents. A novel palladium-catalyzed oxidative carbonylation reaction of organoindium reagents by CO gas with desyl chloride as oxidant was developed in supplementation with the classical methods for preparation of carboxylic acid derivatives. Primary, secondary alkyl indium reagents with beta-hydrogens and aryl indium reagents were suitable substrates, and the reaction could be carried out at 60 degrees C under 50 psi CO. Carbonylation of alkyl indium reagents can occur smoothly without additional base. Although the indium reagents were prepared from corresponding Grignard reagents (at low temperature), they displayed full compatibility with various functional groups under the protic reaction conditions. Preliminary mechanistic studies including stoichiometric and catalytic reaction examination provided evidence to support the operation of the mechanism consisted of oxidative addition of deslyl chloride to Pd(0) and quick tautomerization to give a palladium enolate species II (ROPdCl), displacement of the enolate group in II by R(2)OH, followed by CO insertion to give alkoxycarbonyl palladium complex V, which undergoes transmetalation with R(1)(3)In and reductive elimination to afford the product and a Pd(0) species. In this mechanism, the alkoxycarbonyl group was transferred to the palladium center prior to the alkyl group, different from traditional ways initiated from oxidative addition of alkyl halides to a Pd(0) species.