Characterization of the Nucleophilic Allylindium Species Generated from Allyl Bromide and Indium(0) in Aqueous Media

• Published in: European Journal of Organic Chemistry Vol. 2010; no. 28; pp. 5359 - 5363
• Main Authors: Yasuda, Makoto, Haga, Masahiko, Nagaoka, Yasunori, Baba, Akio
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.10.2010; WILEY‐VCH Verlag; Wiley-VCH
• Subjects: Allylation; Aqueous media; Chemistry; Coordination compounds; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Indium; Inorganic chemistry and origins of life; Organic chemistry; Preparations and properties; Reduction; X-ray analysis; Water; Complexation; Nitrogen heterocycle; Benzhydrol derivatives; Organic bromine compounds; Aqueous media; Indium; X ray diffraction; Allylic compound; Allylation; Pyridine derivatives; Characterization; Chemical reduction; Reduction; Indium Organic compounds; Benzenic compound; X-ray analysis; Aqueous solution; Nucleophilicity; Benzaldehyde derivatives; Nucleophile
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201000956

The reductive system of allyl bromide and indium(0) in water generated monoallylindium(III) dibromide and diallylindium(III) bromide. These compounds were characterized by X‐ray analysis after complexation with 3,5‐dibromopyridine or 4‐(dimethylamino)pyridine, respectively. Both isolated complexes showed high nucleophilicity and reacted with benzaldehyde to give the allylation product. The diallylindium(III) bromide was less stable in water than the monoallylindium(III) dibromide. The reaction of the diallylindium(III) with benzhydrol gave a (μ‐alkoxido)indium species that showed nucleophilicity. This result suggests that allyl(μ‐hydroxido)indium also acted as a nucleophile in an aqueous Barbie‐type reaction system. Allylindium species were generated from allylic halide/In0 in aqueous media. Monoallylindium dibromide, diallylindium bromide, and indium alkoxide are realspecies in the reaction course. They were characterized by X‐ray crystallography, and their structures and reactivities were revealed.