Palladium-Catalyzed Cross-Coupling Reactions of in Situ Generated Allylindium Reagents with Aryl Halides

Lee, Phil Ho; Sung, Sun-young; Lee, Kooyeon

doi:10.1021/ol016532h

Cited by 95 publications

(25 citation statements)

References 26 publications

(8 reference statements)

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“…Since the beginning of the past decade, we have engaged in the development of efficient transition metal‐catalyzed cross‐coupling reactions using organoindium reagents . In the course of our continuing interest in this area, we have recently described Pd‐catalyzed intermolecular homo‐coupling reactions between aryl and heteroaryl halides .…”

Section: Methodsmentioning

confidence: 99%

ChemInform Abstract: Palladium‐Catalyzed Intramolecular Coupling Reactions Between Vinyl Bromides, Aryl and Vinyl Halides, and Aryl Iodides Mediated by Indium: Preparation of Five‐ to Eight‐Membered Carbocycles and Hetereocycles.

et al. 2015

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Vinyl-vinyl, aryl-vinyl, and aryl-aryl bond-forming reactions are one of the most significant methods in synthetic organic chemistry, because the structures produced by the reaction are the general moieties found in natural products, biologically active compounds, and electronic organic materials.1 To date, transition metal-catalyzed coupling reactions have been widely used for the formation of these bonds. Thus, the synthetic approaches for the homo-and cross-coupling reactions using an array of transition metals have so far been reported.2 Among them, the original and most broadly used method is the Ullmann reaction, which is homo-coupling reaction between aryl halides mediated by copper.1f,3 However, the stoichiometric amounts of copper reagent, high temperature, and poor substrate scope are the limitations of the reaction. Moreover, although a variety of aryl-aryl bond-forming reactions via intermolecular coupling reaction have been developed, the intramolecular coupling reaction for vinyl-vinyl, aryl-vinyl, and aryl-aryl bond formation is still rare. 4 These results prompted us to investigate the intramolecular coupling reaction.Since the beginning of the past decade, we have engaged in the development of efficient transition metal-catalyzed crosscoupling reactions using organoindium reagents. 5 In the course of our continuing interest in this area, we have recently described Pd-catalyzed intermolecular homo-coupling reactions between aryl and heteroaryl halides. 6 Based on these results, we report herein Pd-catalyzed intramolecular coupling reactions between vinyl bromides, aryl and vinyl halides, and aryl iodides mediated by indium, producing medium-sized carbocycles and heterocycles, particularly seven-and eightmembered ring compounds that have received significant attention due to the ubiquity of their skeletons in many natural products (Scheme 1).An initial attempt to achieve the intramolecular coupling reaction is conducted with bis(vinyl bromide) 1a obtained from ethyl phenylsulfonylacetate and 2,3-dibromo-1-propene. Pd on charcoal is the best catalyst among several catalysts [Pd(PPh 3 ) 4 , Pd 2 dba 3 CHCl 3 , and (π-allyl) 2 PdCl 2 ]. DMF (0.5 M) proved to be the solvent of choice among THF, THF-H 2 O, DMF, DMF-H 2 O, PhCH 3 , and CH 3 CN. The best results were obtained with Pd/C (10 mol%), indium (2.0 equiv), and LiCl (3.0 equiv) in DMF (0.5 M) at 100 C for 3 h under nitrogen atmosphere, producing the cyclized product 2a in 61% yield. Moreover, high dilution conditions were not required despite of intramolecular reaction. Additives such as LiBr, LiI, KBr, and KI failed to afford the coupling product in good yield. Control experiments revealed that no coupling product was observed without indium and Pd/C. The use of stoichiometric amounts of indium accelerated the coupling reaction, and indium (10 mol%) resulted in sluggish reaction. Bis(vinyl bromide) 1a pretreated with indium and lithium chloride in DMF was subjected to Pd/C to produce 2a in low yield, indicating that arylindium reagent was not...

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Section: Methodsmentioning

confidence: 99%

ChemInform Abstract: Palladium‐Catalyzed Intramolecular Coupling Reactions Between Vinyl Bromides, Aryl and Vinyl Halides, and Aryl Iodides Mediated by Indium: Preparation of Five‐ to Eight‐Membered Carbocycles and Hetereocycles.

et al. 2015

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“…In recent years, indium (III) organometallic compounds have demonstrated their great potential in transition-metal (Pd or Ni) catalyzed cross-coupling chemistry. [6][7][8][9][10][11][12] Besides their high reactivity such reagents exhibit a good functional group compatibility, a low toxicity and ease of handling.…”

Section: Methodsmentioning

confidence: 99%

Pd-Catalyzed Cross-Coupling of Chloroarene-Cr(CO)3 Complexes with Stabilized Organoindium(III) Reagents Under Remarkably Mild Conditions

Gotov¹,

Kaufmann²,

Schumann³

et al. 2002

Synlett

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The palladium catalyzed cross-methylation of intramolecularly stabilized dimethylindium (III) compounds (3 and 4) with different chloroarene-Cr(CO) 3 complexes have been studied. Under mild conditions (40 °C in THF, 3 h) high yields (up to 96%) of the coupling products were obtained in the presence of 1-10 mol% of PdCl 2 (PPh 3 ) 2 . With MeMgCl almost no conversion was observed under the same conditions.

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“…The residue was adsorbed onto silica gel then purication by ash chromatography (diethyl ether : methanol, 98.5 : 1.5 then THF) afforded the title compound as a light pink solid (0.32 g, 90%). 1 H NMR (400 MHz, tert-Butyl 2-(4-methallylphenyl)-propionate (17). The general procedure was employed for the allylation of tert-butyl MIDA (36 mg, 0.10 mmol) using 2-methylallyl bromide (0.020 mL, 0.20 mmol).…”

Section: General Procedures For Allylation Of Mida Boronatesmentioning

confidence: 99%

MIDA boronate allylation – synthesis of ibuprofen

et al. 2020

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Palladium-Catalyzed Cross-Coupling Reactions of in Situ Generated Allylindium Reagents with Aryl Halides

Cited by 95 publications

References 26 publications

ChemInform Abstract: Palladium‐Catalyzed Intramolecular Coupling Reactions Between Vinyl Bromides, Aryl and Vinyl Halides, and Aryl Iodides Mediated by Indium: Preparation of Five‐ to Eight‐Membered Carbocycles and Hetereocycles.

ChemInform Abstract: Palladium‐Catalyzed Intramolecular Coupling Reactions Between Vinyl Bromides, Aryl and Vinyl Halides, and Aryl Iodides Mediated by Indium: Preparation of Five‐ to Eight‐Membered Carbocycles and Hetereocycles.

Pd-Catalyzed Cross-Coupling of Chloroarene-Cr(CO)3 Complexes with Stabilized Organoindium(III) Reagents Under Remarkably Mild Conditions

MIDA boronate allylation – synthesis of ibuprofen

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