Synthetic method for the preparation of 2-aminomethyl-1,3-diene derivatives through indium-mediated 1,3-butadien-2-ylation of imines.

An efficient method for the preparation of a variety of 2-aminomethyl-1,3-dienes was developed through the reaction of imines with organoindium reagent generated in situ from indium and 1,3-dibromo-2-butyne. Three-component reactions of aldehydes, amines, and organoindium reagents gave successful results in a one-pot process.

Palladium-catalyzed cross-couplings of 1,3-butadien-2-yl species with organoindiums generated from allenylmethyl bromide and indium.

An organoindium generated from the reaction of indium with allenylmethyl bromide is an efficient nucleophile in Pd-catalyzed cross-couplings, producing 1,3-butadienes; cross-couplings followed by [4 + 2] cycloadditions gave six-membered carbocycles in a one-pot process.

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.

Inter- and intramolecular palladium-catalyzed allyl cross-coupling reactions using allylindium generated in situ from allyl acetates, indium, and indium trichloride.

Inter- and intramolecular palladium-catalyzed allyl cross-coupling reactions using allylindium generated in situ by treatment of allyl acetates with indium and indium trichloride in the presence of Pd(0) catalyst and nBuNMe(2) in DMF were successfully demonstrated. Allylindium species generated in situ by reductive transmetalation of pi-allylpalladium(II) complexes, obtained from a variety of allyl acetates in the presence of Pd(0) catalyst together with indium and indium trichloride, were found to be capable of acting as effective nucleophilic coupling partners in Pd-catalyzed cross-coupling reactions. A variety of allyl acetates such as but-1-en-3-yl acetate, crotyl acetate, and 2-methylallyl acetate afforded the corresponding allylic compounds in good yields in cross-coupling reactions.

Regioselective allylgallation of terminal alkynes.

The reactions of terminal alkynes with allylgallium reagents generated in situ from gallium and allyl bromides gave the corresponding 1,4-dienes in good yield via Markovnikov addition in THF at 70 degrees C.

Palladium-catalyzed inter- and intramolecular coupling reactions of aryl and vinyl halides mediated by indium.

Treatment of aryl and vinyl halides with 50 mol % of 100 mesh indium, 2.5 mol % of Pd-C, and 1.5 equiv of LiCl under mild conditions (DMF, 100 degrees C, 1-3 h) could produce coupling products efficiently in good to excellent yields in which the C(sp2)-C(sp2) bond was formed.

Cyclization of 1-bromo-2,7- and 1-bromo-2,8-enynes mediated by indium.

[reaction: see text] The cyclization of 1-bromo-2,7- and 1-bromo-2,8-enynes mediated by indium in DMF produced five- and six-membered cyclic compounds. Although KI was a necessary additive in the cyclization of terminal 1-bromo-2,7-enynes to give the desired products at 25 degrees C, reactions of terminal 1-bromo-2,8-enynes and internal 1-bromo-2,7-enynes with indium proceeded at 100 degrees C in DMF without KI. After cyclizations, subsequent cross-coupling reaction and iodolysis increase the usefulness of this reaction.

Highly efficient Pd-catalyzed carbonylative cross-coupling reactions with tetraorganoindates.

Tetraorganoindates, which were prepared easily from the reaction of 1 equiv of InCl(3) with 4 equiv of organometallics, could be employed as effective nucleophilic cross-coupling partners in Pd-catalyzed carbonylative cross-coupling reactions with a variety of organic electrophiles. The present method gave unsymmetrical ketones and 1,4-diacylbenzenes in good yields with highly efficient transfer of almost all the organic groups attached to the indium under a carbon monoxide atmosphere in THF at 60 degrees C.

Highly efficient iridium-catalyzed oxidation of organosilanes to silanols.

Hydrolytic oxidation of organosilanes to the corresponding silanols can be performed highly efficiently with a catalyst system of [IrCl(C(8)H(12))](2) under essentially neutral and mild conditions, and various types of silanols are produced in good to excellent yields.

Tetraorganoindates as nucleophilic coupling partners in Pd-catalyzed cross-coupling reactions.

In situ-generated tetraorganoindate complexes from the reaction of 1 equiv of indium trichloride with 4 equiv of appropriate organometallics are efficient nucleophiles in Pd-catalyzed cross-coupling reactions. In this novel reaction tetraorganoindates containing methyl, 1 degree- and 2 degree-alkyl, vinyl, alkynyl, and aryl groups transfer the four organic groups to a variety of electrophiles with high atom efficiency. [reaction: see text]

Palladium-catalyzed homocoupling reaction of 1-iodoalkynes: a simple and efficient synthesis of symmetrical 1,3-diynes.

This paper describes a highly efficient synthetic method of symmetrical 1,3-diynes from 1-iodoalkynes in the presence of 4 mol % Pd(PPh(3))(4) in DMF at room temperature under a nitrogen atmosphere without any use of additives and other metals.

Highly efficient 1,4-addition of 1,3-diesters to conjugated enones by In/TMSCl.

Organoindium reagents derived from indium and diethyl bromomalonates were added to a wide range of conjugated enones in a 1,4-fashion in the presence of TMSCl under mild conditions, and corresponding oxo-1,3-diesters were obtained in good to excellent yields.