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

Nathan C. Tice; Sean Parkin; John P. Selegue

doi:10.1016/j.jorganchem.2006.10.015

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

Nathan C. Tice, Sean Parkin, John P. Selegue

Chemistry

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	791-800
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	692
Issue number	4
DOIs	https://doi.org/10.1016/j.jorganchem.2006.10.015
State	Published - Jan 15 2007

Bibliographical note

Funding Information:
We thank the Research Corporation and the University of Kentucky Research Challenge Trust Fund for support. Appendix A

Keywords

Amine-cyanoborane adduct
Ammonium cyanoborohydride
Ferrocene
NMR spectroscopy
Reductive amination
X-ray crystal structure

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.jorganchem.2006.10.015

Cite this

@article{7b95cbd04f1344ee8dada77303f05d76,

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

abstract = "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.",

keywords = "Amine-cyanoborane adduct, Ammonium cyanoborohydride, Ferrocene, NMR spectroscopy, Reductive amination, X-ray crystal structure",

author = "Tice, {Nathan C.} and Sean Parkin and Selegue, {John P.}",

note = "Funding Information: We thank the Research Corporation and the University of Kentucky Research Challenge Trust Fund for support. Appendix A ",

year = "2007",

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doi = "10.1016/j.jorganchem.2006.10.015",

language = "English",

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Synthesis, characterization and crystal structures of boron-containing intermediates in the reductive amination of ferrocenecarboxaldehyde to a bis(ferrocenylmethyl) amine. / Tice, Nathan C.; Parkin, Sean ; Selegue, John P.
In: Journal of Organometallic Chemistry, Vol. 692, No. 4, 15.01.2007, p. 791-800.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Synthesis, characterization and crystal structures of boron-containing intermediates in the reductive amination of ferrocenecarboxaldehyde to a bis(ferrocenylmethyl) amine

AU - Tice, Nathan C.

AU - Parkin, Sean

AU - Selegue, John P.

N1 - Funding Information: We thank the Research Corporation and the University of Kentucky Research Challenge Trust Fund for support. Appendix A

PY - 2007/1/15

Y1 - 2007/1/15

N2 - 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.

AB - 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.

KW - Amine-cyanoborane adduct

KW - Ammonium cyanoborohydride

KW - Ferrocene

KW - NMR spectroscopy

KW - Reductive amination

KW - X-ray crystal structure

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DO - 10.1016/j.jorganchem.2006.10.015

M3 - Article

AN - SCOPUS:33845912960

SN - 0022-328X

VL - 692

SP - 791

EP - 800

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 4

ER -

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

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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