title: Reaction of InCl3 with various reducing agents: InCl3-NaBH4-mediated reduction of aromatic and aliphatic nitriles to primary amines.
abstract: 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. Nitriles underwent reduction to primary amines under optimized conditions at 25 °C using 1 equiv of anhydrous InCl(3) with 3 equiv of NaBH(4) in THF. A variety of aromatic, heteroaromatic, and aliphatic nitriles were reduced to their corresponding primary amine in 70-99% isolated yields. Alkyl halide and nitrile functional groups were reduced in tandem by utilizing the reductive capabilities of both HInCl(2) and BH(3)·THF in a one-pot reaction. Finally, the selective reduction of the carbon bromine bond in the presence of nitriles was achieved by generating HInCl(2) via the reduction InCl(3) with NaBH(4) in CH(3)CN or with lithium dimethylaminoborohydride (MeLAB) in THF.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Santa Cruz, 1156 High Street, Santa Cruz, California 95064, United States.
authors.forename: Jaime Z
authors.initials: JZ
authors.lastname: Saavedra
authors.forename: Angel
authors.initials: A
authors.lastname: Resendez
authors.forename: Alexander
authors.initials: A
authors.lastname: Rovira
authors.forename: Scott
authors.initials: S
authors.lastname: Eagon
authors.forename: Dustin
authors.initials: D
authors.lastname: Haddenham
authors.forename: Bakthan
authors.initials: B
authors.lastname: Singaram