Synthesis, characterization and crystal structures of boron-containing intermediates in the reductive amination of ferrocenecarboxaldehyde to a bis(ferrocenylmethyl) amine

Reaction of ferrocenecarboxaldehyde with aqueous methylamine leads to [(methylimino)methyl]ferrocene, which is reduced to N-(ferrocenylmethyl)-N-methylamine by NaBH4. This amine reacts with ferrocenecarboxaldehyde and NaCNBH3 to give the tertiary ammonium salt, di(N-(ferrocenylmethyl))-N-methylammonium cyanoborohydride. Hydrolysis of the NaCNBH3 reaction mixture produces the free amine, di(N-(ferrocenylmethyl))-N-methylamine. Thermolysis of di(N-(ferrocenylmethyl))-N-methylammonium cyanoborohydride in refluxing tetrahydrofuran converts it to the cyanoborane adduct, di(N-ferrocenylmethyl)-N-methylamine–cyanoborane, with elimination of H2. The new compounds are fully characterized by using spectroscopic and physical methods, including X-ray crystal structure determinations of di(N-(ferrocenylmethyl))-N-methylammonium cyanoborohydride, di(N-(ferrocenylmethyl))-N-methylamine, and di(N-(ferrocenylmethyl))-N-methylamine–cyanoborane.

Graphical abstractReductive amination of ferrocenecarboxaldehyde with N-(ferrocenylmethyl)-N-methylamine and NaCNBH3 gives the tertiary ammonium salt, di(N-(ferrocenylmethyl))-N-methylammonium cyanoborohydride. Hydrolysis of the reaction mixture produces the amine, di(N-(ferrocenylmethyl))-N-methylamine. Thermolysis of di(N-(ferrocenylmethyl))-N-methylammonium cyanoborohydride in refluxing tetrahydrofuran converts it to the cyanoborane adduct, di(N-ferrocenylmethyl)-N-methylamine–cyanoborane, with elimination of H2.Figure optionsDownload full-size imageDownload as PowerPoint slide