Indium Iodide Research Articles

Palladium—Indium Iodide‐Mediated Allylation and Propargylation of Glyoxylic Oxime Ether and Hydrazone: The Role of Water in Directing the Diastereoselective Allylation.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Spectroscopic Studies of Diatomic Indium Halides

A critical review of the available spectroscopic information about diatomic indium halides has been performed. The literature was surveyed till early 2002 and the data on the molecular constants for the ground state, as well as excited states of these molecules has been presented. A brief discussion on the dissociation energies, ionization potentials, and the nature of the bonding in the ground state is given. The energy level diagram and Rydberg–Klein–Rees potential curves for the different electronic states of these molecules are also presented. Mechanism of laser emission/fluorescence due to atomic indium in the ultraviolet photodissociation of indium monohalides has also been discussed.

Control of Diastereoselectivity in the Crotylation and Cinnamylation of Aldehydes by the Selection of Ligands on Allylic Indium Reagents.

AbstractFor Abstract see ChemInform Abstract in Full Text.

A New Synthesis of Pyrroles by the Condensation of Cyclopropenes and Nitriles Mediated by Gallium(III) and Indium(III) Salts.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Palladium-indium iodide-mediated allylation and propargylation of glyoxylic oxime ether and hydrazone: the role of water in directing the diastereoselective allylation.

Allylation and propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(0) complex and indium(I) iodide were studied. Excellent diastereoselectivities in allylation were achieved in the presence of water, although low diastereoselectivities were observed in the absence of water. Propargylation of glyoxylic oxime ether proceeded with good diastereoselectivities in the presence of LiBr or LiCl.

Indium(III) Halide Mediated S N 2′ Reactions of Substituted Allenols: Synthesis of 2-Halo-1,3-dienes

Treatment of various substituted allenols with indium(III) halide in benzene gave (Z)- or (E)-2-halo-1,3-dienes in moderate to good yields. In most cases, (2Z)-halo-1,3-dienes were obtained as major products.

Indium(I) Iodide-Promoted Cleavage of Dialkyl Disulfides and Subsequent Michael Addition of Thiolate Anions to Conjugated Carbonyl Compounds

Indium(I) iodide promotes cleavage of dialkyl disulfides generating thiolate anions which then undergo facile addition to α, β -unsaturated ketones, aldehydes, carboxylic esters and nitriles under neutral conditions producing corresponding β-keto or β-cyano sulfides in high yields. There are several examples of dialkyl/diaryl disulfides and activated alkenes participating in this reaction.

Indium(I) trifluoromethanesulfonate and other soluble salts for univalent indium chemistry.

Herein we report the synthesis, structure and preliminary reactivity studies of a series of unusually soluble indium(i) salts that are improved alternatives to indium(i) halide reagents.

The reactivity of gallium(i) and indium(i) halides towards bipyridines, terpyridines, imino-substituted pyridines and bis(imino)acenaphthenes

“GaI” reacts with 2,2′-bipyridine (bipy) to give salts of composition [Ga(bipy)3][I]3, [{(bipy)2Ga}2(μ-OH)2]2[Ga2I6][I]6 or [{(bipy)2Ga}2(μ-OH)2][I]4, depending upon the reaction conditions. “GaI” also reacts with 4′-phenyl-2,2′∶6′,2″-terpyridine (Phterpy) to give the salt [GaI2(Phterpy)][I]. When “GaI” is treated with the imino-substituted pyridines RNC(H)Py, Py = 2-pyridyl, R = Ar (C6H3Pri2-2,6) or But, a reductive coupling of the CN functionality occurs to give the diamido-digallium(III) complexes [{I2Ga[η2-(Py)(NR)C(H)]}2]. In contrast, InCl reacts with ArNC(H)Py to give an adduct, [InCl3(THF){η2-ArNC(H)Py}], via disproportionation of the metal halide. Similarly, the reaction of the bis(imino)pyridine, 2,6-{ArNC(Me)}2(NC5H3), bimpy, with “GaI” affords the salt [GaI2(bimpy)][GaI4]. Finally, the reaction of bis(2,6-diisopropylphenylimino)acenaphthene (ArBIAN) with “GaI” leads to a paramagnetic Ga(III) complex [GaI2(ArBIAN)˙]. The X-ray crystal structures of all prepared complexes are reported.

Regioselectivity in Palladium—Indium Iodide‐Mediated Allylation Reaction of Glyoxylic Oxime Ether and N‐Sulfonylimine.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Remote Stereocontrol Using Allylstannanes: Reversal in Stereoselectivity Using Indium(III) and Bismuth(III) Halides as Promoters.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Indium(I) Iodide Mediated Cleavage of Diphenyl Diselenide. An Efficient One‐Pot Procedure for the Synthesis of Unsymmetrical Diorganyl Selenides.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Regioselectivity in palladium-indium iodide-mediated allylation reaction of glyoxylic oxime ether and N-sulfonylimine.

Allylation reaction of electron-deficient imines with allylic alcohol derivatives in the presence of a catalytic amount of palladium(0) complex and indium(I) iodide was studied. The reversibility of allylation was observed in the reaction of glyoxylic oxime ether having camphorsultam. As the important effect of water on regioselectivity, the gamma-adducts were kinetically formed from monosubstituted allylic reagents in the presence of water. The selective formation of thermodynamically stable alpha-adducts was observed in anhydrous THF. In contrast, the allylation of N-sulfonylimine gave the gamma-adducts with high regioselectivities even under anhydrous reaction conditions.

Stereo‐ and Regioselectivity of Pd0/InI‐Mediated Allylic Additions to Aldehydes and Ketones. In situ Generation of Allylindium(III) Intermediates from N‐Acylnitroso Diels—Alder Cycloadducts and 1‐Amino‐4‐acetoxycyclopentenes.

Acylnitroso Diels-Alder cycloadduct (11, 37, and 45)- and cyclopentenyl acetate (8 and 9)-derived allylindium(III) species were generated in situ from palladium(0) catalysts and indium(I) iodide, and the stereo- and regiochemistry of their additions to aldehydes and ketones were investigated. Solvent, catalyst, and ionic effects were examined for the reaction of N-acetyl cycloadduct (11) and benzyloxyacetaldehyde (10). The solvent mixture of THF/H(2)O with Pd(OAc)(2).PPh(3) catalysis was found to be optimal. The addition of N-acetyl cycloadduct to aliphatic aldehydes afforded products in good yields and high regio- and stereoselectivity, with the cis-1,4-isomers constituting 90-95% of the products. The reactions with N-Boc (37a) and N-methylcarbamate (37b) cycloadducts also gave the cis-1,4-products predominantly. The same regio- and stereoselectivity applied to the reactions of 4-acetoxy-1-(N-hydroxyphenyacetamido)cyclopentene (8). 4-Acetoxy-1-phenylacetamidocyclopentene (9), however, afforded trans-1,4-products exclusively. Mechanistic speculations involving chelated transition states are described.

Indium(III) halides-catalyzed preparation of ferrocene-dihydropyrimidinones

Indium(III) halides (chloride and bromide) catalyse the three-component Biginelli coupling of ferrocenyl-1,3-diketones, aldehydes and urea (or thiourea) to give 5-ferrocenoyl-3,4-dihydropyrimidinones. 4-Ferrocenyl-3,4-dihydropyrimidinones were obtained from alkyl-acetoacetates, formylferrocene and urea. The tricyclic compound, 13-ferrocenecarbonyl-9-methyl-11-oxo-8-oxa-10,12-diazatricyclo [7.3.1.0 2,7]trideca-2,4-6-triene, was synthesized from 1-ferrocenyl-1,3-butanedione, salicilaldehyde and urea.

Dimethyl sulfoxide solvates of the aluminium(iii), gallium(iii) and indium(iii) ions. A crystallographic, EXAFS and vibrational spectroscopic studyElectronic supplementary information (ESI) available: normalized X-ray absorption edges, calculated separate contributions of the different scattering paths to the EXAFS oscillations for the dimethyl sulfoxide solvated gallium(iii) and indium(iii) ions in the solid state and solution; correlation between compression ratio (s/h) and bond lengths

The isostructural hexakis(dimethyl sulfoxide)-aluminium(III), -gallium(III) and -indium(III) iodides crystallise in the trigonal space group R (no. 148), Z = 3, at 295 ± 1 K. The metal ions are located in a symmetry site with M–O bond distances of 1.894(4), 1.974(4) and 2.145(3) A, and M–O–S bond angles of 127.1(3), 124.1(3) and 123.1(2)°, for M = Al, Ga and In, respectively. The unit cell parameters are a = 10.762(2), c = 24.599(3) A, V = 2467.2(5) A3 for [Al(OS(CH3)2)6]I3, a = 10.927(2), c = 23.868(4) A, V = 2468.1(6) A3 for [Ga(OS(CH3)2)6]I3, and a = 11.358(2), c = 21.512(4) A, V = 2403.5(7) A3 for [In(OS(CH3)2)6]I3. The increasing compression of the octahedral MO6 coordination entities along one three-fold axis for M = Al, Ga and In, respectively, explains why the largest ion indium(III) has the smallest unit cell volume. EXAFS measurements on the dimethyl sulfoxide solvated gallium(III) and indium(III) ions in solution and in the solid perchlorate and trifluoromethanesulfonate salts, show similar bond distances as in the solid iodide solvates. Raman and infrared spectra have been recorded for the hexakis(dimethyl sulfoxide)metal(III) iodides and the nature of the metal–sulfoxide bond has been evaluated by normal coordinate methods. The symmetric and asymmetric M–O stretching modes correspond to the vibrational frequencies 465 and 540 cm−1 for [Al(OS(CH3)2)6]I3, 491 and 495 cm−1 for [Ga(OS(CH3)2)6]I3, and 444 and 440 cm−1 for [In(OS(CH3)2)6]I3, respectively.

Remote stereocontrol using allylstannanes: reversal in stereoselectivity using indium(III) and bismuth(III) halides as promoters.

Allyl-indium(III) and -bismuth(III) dihalides, generated by transmetallation of 5-benzyloxy-4-methylpent-2-enyl(tributyl)stannane 1, react with aldehydes with useful levels of 1,5-stereocontrol, a 93:7 ratio of 1,5-epimers in favour of the 1,5-anti-(E)-stereoisomers 7 and 11 typically being obtained using bismuth(III) iodide. The 4-benzyloxypent-2-enylstannane 4 similarly gives the 1,5-syn-(E)-hex-3-enols 13 also with ca. 93:7, stereoselectivity.

A new synthesis of pyrroles by the condensation of cyclopropenes and nitriles mediated by gallium(III) and indium(III) salts.

Gallium(III) and indium(III) halides were found to mediate the condensation of cyclopropenes and nitriles to give pyrrole derivatives in moderate yields. When excess nitrile was present, diazepine was also formed.

Control of diastereoselectivity in the crotylation and cinnamylation of aldehydes by the selection of ligands on allylic indium reagents.

Diastereoselective couplings of salicylaldehyde, anisaldehyde and 2-pyridylaldehyde with crotyl- and cinnamylindium reagents were studied. The syl/anti selectivity was found to depend largely on the ligands on the indium atom of the allylic indium reagents. A syn-selective cinnamylation of salicylaldehyde was realized by the combination of cinnamyl acetate and indium(I) iodide, whereas an anti-selective coupling with salicylaldehyde was achieved by the indium trichloride/aluminium-mediated cinnamylation.

Indium(I) Iodide-Mediated Chemo-,Regio-, and Stereoselective Hydro­telluration of 2-Alkyn-1-olDerivatives

Indium(I) iodide promotes the rigorous chemo-, regio-, and stereoselectivehydrotelluration of 2-alkyn-1-ol derivatives with diphenylditelluride.The Markovnikov adducts with stereochemistry corresponding to an anti addition of the tellurol constituentsacross the triple bond were obtained in good yields.