Organic azides are easily reduced to the corresponding amines by reaction with dichloroindium hydride under very mild conditions and in a highly chemoselective fashion. Gamma-azidonitriles give rise to outstanding five-membered cyclizations affording pyrrolidin-2-imines. A rationalization of the overall experimental data cannot exclude the occurrence of competitive radical and nonradical pathways, but certain results are, however, soundly consistent with the intermediacy of indium-bound nitrogen-centered radicals. [reaction: see text]
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Reaction of InCl3 with various reducing agents: InCl3-NaBH4-mediated reduction of aromatic and aliphatic nitriles to primary amines.
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Department of Chemistry and Biochemistry, University of California, Santa Cruz, 1156 High Street, Santa Cruz, California 95064, United States.
While alternative methods of preparing dichloroindium hydride (HInCl(2)) via the in situ reduction of InCl(3) using lithium amino borohydride (LAB) were explored, generation of HInCl(2) from the reduction of InCl(3) by sodium borohydride (NaBH(4)) was also re-evaluated for comparison. The reductive capability of the InCl(3)/NaBH(4) system was found to be highly dependent on the solvent used. Investigation by (11)B NMR spectroscopic analyses indicated that the reaction of InCl(3) with NaBH(4) in THF generates HInCl(2) along with borane-tetrahydrofuran (BH(3)·THF) in situ.
View Article and Find Full Text PDFGeneration of allylic indium by hydroindation of 1,3-dienes and one-pot reaction with carbonyl compounds.
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Research Center for Environmental Preservation, Osaka University, 2-4 Yamadaoka, Suita, Osaka 565-0871, Japan.
A hydroindation of 1,3-dienes by dichloroindium hydride (HInCl2) generates allylic indiums that react with carbonyl or imine moieties in a one-pot treatment. The former reaction proceeds in a radical manner, and the latter is ionic allylation. Moreover, both reactions require no additives such as radical initiators, Lewis acids, or transition metal catalysts.
View Article and Find Full Text PDFReaction of azides with dichloroindium hydride: very mild production of amines and pyrrolidin-2-imines through possible indium-aminyl radicals.
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Dipartimento di Chimica Organica A. Mangini, Università di Bologna, Viale Risorgimento 4, I-40136 Bologna, Italy.
Organic azides are easily reduced to the corresponding amines by reaction with dichloroindium hydride under very mild conditions and in a highly chemoselective fashion. Gamma-azidonitriles give rise to outstanding five-membered cyclizations affording pyrrolidin-2-imines. A rationalization of the overall experimental data cannot exclude the occurrence of competitive radical and nonradical pathways, but certain results are, however, soundly consistent with the intermediacy of indium-bound nitrogen-centered radicals.
View Article and Find Full Text PDFTrans-hydrometalation of alkynes by a combination of InCl3 and DIBAL-H: one-pot access to functionalized (Z)-alkenes.
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Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 606-8501, Japan.
[reaction: see text] Triethylborane-induced hydrometalation of alkynes proceeds in an anti manner to afford the corresponding (Z)-alkenylmetal compounds stereoselectively, where dichloroindium hydride would play a key role. A variety of functional groups including hydroxy, carbonyl, and carboxy groups were tolerant under the reaction conditions. Following iodolysis and cross-coupling reaction of the (Z)-alkenylmetal species show the usefulness of this strategy.
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