Allylation of methylenecyclopropanes with allylindium reagents

Methylenecyclopropanes carrying a hydroxymethyl group at the ring underwent stereoselective allylindation with allylindium sesquiiodide to afford the allylated products, in which the allyl group was delivered at the external sp² carbon via cyclopropylindium intermediates. The reaction of ethyl 2-cyclopropylideneacetate and triallylindium afforded the 1,4-adduct along with dimeric products.     

A novel nucleophilic substitution of in situ generated 3-tert-butyldimethyl- silyloxyalk-2-enylsulfonium salts with allylindium reagents

[reaction: see text] In situ generated 3-tert-butyldimethylsilyloxyalk-2-enylsulfonium salts derived from the reaction of alpha,beta-enones with dimethyl sulfide in the presence of TBSOTf undergo a novel nucleophilic substitution with in situ generated allylindium reagents from indium and allyl halides to give silyl enol ethers of delta,epsilon-unsaturated ketones, which correspond to Michael addition products, in good yields.     

Tandem N-alkylation-C-allylation reaction of alpha-imino esters with organoaluminums and allyltributyltin

On treatment of various alpha-imino esters with organoaluminum reagents and allyltributyltin in the presence of benzoyl peroxide, the tandem reaction proceeded to give the N-alkylation-C-allylation products in good yields. The tandem N-alkyation-C-cyanation also proceeded using silyl or aluminum cyanide to give the aminonitrile in good yield.     

Synthesis of fully-substituted alkenylimidazoles from N-(cyanoalkyl)amides via the In-mediated allylation of nitrile and dehydrative cyclization cascade

The reaction of allylindium reagents and N-(cyanoalkyl)amides afforded fully-substituted 4-alkenylimidazoles in moderate yields via the In-mediated Barbier-type allylation of nitrile and the following dehydrative cyclization cascade.     

A room temperature alternative of the Claisen rearrangement route to ortho allylated phenols: unique reactivity pattern of allylindium reagents

Quinol ethers and quinone monoketals are shown to undergo formal anti-Michael addition reactions with allylindium reagents at room temperature to give only ortho allylated phenols in good yields.     

Synthesis of 4-allylquinazolines from N-(2-cyanoaryl)amides via the In-mediated allylation of nitrile and dehydrative cyclization cascade

The reaction of allylindium reagents and N-(2-cyanoaryl)amides afforded 2-substituted-4-allylquinazolines in good yields via the indium-mediated Barbier-type allylation of nitrile and the following dehydrative cyclization cascade.     

A new enamine synthesis: Allylation-enamination reaction of nitriles with allylindium reagents

The reaction of allylindium reagents with certain nitriles 1 having another electron withdrawing group at the α-position affords the corresponding allylation-enamination products 2 in high to good yields.     

Iodine-catalyzed Michael addition of mercaptans to α,β-unsaturated ketones under solvent-free conditions

A simple and efficient method for the Michael reaction between various mercaptans and α,β-unsaturated ketones using a catalytic amount of iodine (5 mol %) to generate the 1,4-adduct has been reported. The significant features of the iodine catalyzed Michael addition are (a) operational simplicity, (b) inexpensive reagents, (c) high yields of products, (d) the use of relatively low or nontoxic reagents and (e) solvent-free conditions.     

INDIUM-MEDIATED BARBIER REACTIONS OF AZIDES: A FACILE SYNTHESIS OF N-ALLYLAMINE DERIVATIVES

ABSTRACT

N-Allylic amines are conveniently prepared in high yields by the reaction of azides with allylindium reagents in the presence of sodium iodide in DMF at ambient temperature.     

Palladium-catalyzed cross-coupling reactions of in situ generated allylindium reagents with aryl halides

[reaction: see text] In situ generated allylindium reagents from the reaction of 1 equiv of indium with 1.5 equiv of allyl halides could be effective cross-coupling partners in palladium-catalyzed cross-coupling reactions to aryl halides. The best results were obtained with 2% Pd(2)dba(3)CHCl(3) and 16% Ph(3)P in the presence of 3 equiv of LiCl in DMF at 100 degrees C.     

Chiral (S)‐(+) 1‐Substituted Aryl‐4‐(1‐phenyl) Ethylformamido‐5‐amino‐1,2,3‐triazole: A New Class of Chiral Ligands for the Silver(I)‐Promoted Enantioselective Allylation of Aldehydes

Some novel chiral ligands, (S)‐(+) 1‐substituted aryl‐4‐(1‐phenyl) ethylformamido‐5‐amino‐1,2,3‐triazoles, were prepared starting from 1‐substituted aryl‐4‐ethoxycarbonyl‐5‐amino‐1,2,3‐triazoles and other reagents. They were used as catalytic chiral ligands in the silver (I)‐promoted enantioselective allylation reaction of aldehydes with allyltributyltin.     

Addition of allylindium reagents to acyl phosphonates: synthesis of tertiary α-hydroxy alkylphosphonates

Treatment of acyl phosphonates with allylindium reagents in the presence of acetic acid afforded the corresponding α-hydroxy alkylphosphonates in good yields under mild conditions.     

Allylindation of cyclopropenes in organic and aqueous media: switching the regio- and stereoselectivity based on the chelation with a hydroxyl group and the crystal structure of the cyclopropylindium product

Hydroxy-bearing cyclopropenes react with allylindium reagents to undergo clean allylindation both in organic and aqueous media, in which the chelation of the hydroxyl group to indium plays the central role. The regio- and stereoselectivity have been regulated both by the location of the hydroxyl group in the molecules and the reaction solvents. In particular, the allylindation in water shows marked differences from that in organic solvents; the regio- and stereoselectivity have totally been reversed compared with those in organic solvents. Unusually stable cyclopropyl-indium compounds have been isolated from the reaction of 1-(omega-hydroxyalkyl)cyclopropenes and the structure has fully been established by X-ray crystallography.     

Xantphos as an efficient ligand for palladium-catalyzed cross-coupling reactions of aryl bromides and triflates with allyl acetates and indium

Xantphos was found to be an efficient ligand for palladium-catalyzed allyl cross-coupling reactions of aryl bromides and triflates with allylindium reagents generated in situ from allyl acetates and indium. These reactions occur in high yield with good functional group tolerance.     

Efficient synthetic method of multisubstituted allenes from the reactions of allylindium reagents with 3 degree-propargyl alcohols

An efficient synthetic method of tri- and tetra-substituted allenes having an allyl and methallyl group was developed by the reactions of allylindium reagents generated in situ from indium and allyl bromides with 3 degree-propargyl alcohols.     

Addition of Allylindium Reagents to α-Iminotrifluoroethyl-phosphonates: Synthesis of CF3-Containing α-Aminoalkylphosphonates

Treatment of α-iminotrifluoroethylphosphonates with allylindium reagents in the presence of acetic acid afforded the corresponding CF₃ -containing α-aminoalkylphosphonates in high yields (83–97%) under mild conditions.     

Stereoselective allylation of azirines with allylindium reagents

Allylindium reagents allylated azirines to give allylaziridines in good yields. The delivery of the allyl group was well regulated by the substituents at the C³-carbon of azirines. The cis-allylation with respect to the substituent was realized with azirines bearing a hydroxylmethyl or an acetoxymethyl group due to the chelation with allylindium reagents, whereas the trans-allylation was achieved with azirines substituted by a methyl, phenyl, or ester group owing to the steric repulsion.     

Regio-controlled pentadienylation of sulfinylimines by pentadienyltin reagent. Efficient Lewis acid activation of 4-methoxyphenylsulfinyl imines

Nucleophilic addition of pentadienyltin reagent toward N-(4-methoxyphenylsulfinyl)-imine was effectively accelerated by the use of InCl₃ or TMSOTf as a Lewis acid. The former afforded the γ-adduct with high stereoselectivity, while the latter gave the ε-adduct with moderate stereoselectivity, depending on the reaction mechanisms.     

Reductive allylation of poly(chlorotrifluoroethylene)

Treatment of poly(chlorotrifluoroethylene) with allyltin reagents results in the clean replacement of chlorine by the allyl group under free-radical–chain conditions (AIBN, allyltributyltin), affording about a 10% degree of functionalization. An improved method using one-electron reduction of the polymer with cobalt(II) (generated by reduction of chloro(pyridine)bis(dimethylglyoximato)cobalt(III) with Mg) and allyltributyltin gives 50% functionalization. Further modification of the allyl group is realized through hydroboration-oxidation to the alcohol and subsequent Cr(VI) oxidation to the acid. A mechanistic discussion is provided. © John Wiley & Sons, Inc.     

A New Preparative Method for Allylic Indium(III) Reagents by Reductive Transmetalation of pi-Allylpalladium(II) with Indium(I) Salts

A reductive transmetalation of the pi-allylpalladium(II) complexes, generated in situ from a catalytic amount of a palladium(0) complex and a variety of allylic substrates, with indium(I) salts proceeded smoothly in various solvents, providing a new route for allylindium(III) reagents.