Heterobimetallic metallation studies of N,N-dimethylphenylethylamine (DMPEA): benzylic C-H bond cleavage/dimethylamino capture or intact DMPEA complex

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Abstract

Reaction of the sodium monoamido-bisalkylzincate [(TMEDA)Na(TMP)(But)Zn(But)] (TMEDA is N,N,N′,N′-tetramethylethylenediamine; TMP is 2,2,6,6-tetramethylpiperidide) and the related lithium zincate [(PMDETA)Li(TMP)Zn(But)2] (PMDETA is N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) with the sensitive bio-relevant scaffold N,N-dimethylphenylethylamine, DMPEA, afforded the crystalline complexes [(TMEDA)Na(TMP)(NMe2)Zn(But)] and [(PMDETA)Li(NMe2)Zn(But)2], respectively, both of which have been characterized by NMR spectroscopic and X-ray crystallographic studies. Made by reaction of a LiTMP–(TMP)Al(Bui)2 mixture with DMPEA, a third dimethylamino-containing crystalline complex, the aluminate [(THF)Li(TMP)(NMe2)Al(Bui)2] has been similarly characterized. All three complexes can be regarded as products of cleave and capture chemistry whereby metallation at the benzylic position of DMPEA has led to a β-elimination of an anionic Me2N fragment that has been captured by a charge balancing cationic heterobimetallic entity. While a metallated intermediate prior to the elimination has proved elusive in all of these reactions, DMPEA has been captured fully intact in the novel Lewis acid–Lewis base crystalline complex [DMPEA·Li(TMP)Zn(Me)2], which has also been characterized by the aforementioned techniques.
LanguageEnglish
Pages5875-5887
Number of pages13
JournalDalton Transactions
Volume44
Issue number12
Early online date17 Feb 2015
DOIs
Publication statusPublished - 28 Mar 2015

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Thymidine Monophosphate
Crystalline materials
Lewis Bases
Lewis Acids
N,N-dimethylphenylethylamine
Lithium
Scaffolds
Sodium
Nuclear magnetic resonance
X rays

Keywords

  • sodium monoamido-bisalkylzincate [
  • crystalline complexes
  • NMR spectroscopy
  • X-ray crystallography

Cite this

@article{50fd96a19be642cba840eada2597c8f1,
title = "Heterobimetallic metallation studies of N,N-dimethylphenylethylamine (DMPEA): benzylic C-H bond cleavage/dimethylamino capture or intact DMPEA complex",
abstract = "Reaction of the sodium monoamido-bisalkylzincate [(TMEDA)Na(TMP)(But)Zn(But)] (TMEDA is N,N,N′,N′-tetramethylethylenediamine; TMP is 2,2,6,6-tetramethylpiperidide) and the related lithium zincate [(PMDETA)Li(TMP)Zn(But)2] (PMDETA is N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) with the sensitive bio-relevant scaffold N,N-dimethylphenylethylamine, DMPEA, afforded the crystalline complexes [(TMEDA)Na(TMP)(NMe2)Zn(But)] and [(PMDETA)Li(NMe2)Zn(But)2], respectively, both of which have been characterized by NMR spectroscopic and X-ray crystallographic studies. Made by reaction of a LiTMP–(TMP)Al(Bui)2 mixture with DMPEA, a third dimethylamino-containing crystalline complex, the aluminate [(THF)Li(TMP)(NMe2)Al(Bui)2] has been similarly characterized. All three complexes can be regarded as products of cleave and capture chemistry whereby metallation at the benzylic position of DMPEA has led to a β-elimination of an anionic Me2N fragment that has been captured by a charge balancing cationic heterobimetallic entity. While a metallated intermediate prior to the elimination has proved elusive in all of these reactions, DMPEA has been captured fully intact in the novel Lewis acid–Lewis base crystalline complex [DMPEA·Li(TMP)Zn(Me)2], which has also been characterized by the aforementioned techniques.",
keywords = "sodium monoamido-bisalkylzincate [, crystalline complexes, NMR spectroscopy, X-ray crystallography",
author = "Kennedy, {Alan R.} and Mulvey, {Robert E.} and Ramsay, {Donna L.} and Robertson, {Stuart D.}",
year = "2015",
month = "3",
day = "28",
doi = "10.1039/c5dt00247h",
language = "English",
volume = "44",
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journal = "Dalton Transactions",
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T1 - Heterobimetallic metallation studies of N,N-dimethylphenylethylamine (DMPEA)

T2 - Dalton Transactions

AU - Kennedy, Alan R.

AU - Mulvey, Robert E.

AU - Ramsay, Donna L.

AU - Robertson, Stuart D.

PY - 2015/3/28

Y1 - 2015/3/28

N2 - Reaction of the sodium monoamido-bisalkylzincate [(TMEDA)Na(TMP)(But)Zn(But)] (TMEDA is N,N,N′,N′-tetramethylethylenediamine; TMP is 2,2,6,6-tetramethylpiperidide) and the related lithium zincate [(PMDETA)Li(TMP)Zn(But)2] (PMDETA is N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) with the sensitive bio-relevant scaffold N,N-dimethylphenylethylamine, DMPEA, afforded the crystalline complexes [(TMEDA)Na(TMP)(NMe2)Zn(But)] and [(PMDETA)Li(NMe2)Zn(But)2], respectively, both of which have been characterized by NMR spectroscopic and X-ray crystallographic studies. Made by reaction of a LiTMP–(TMP)Al(Bui)2 mixture with DMPEA, a third dimethylamino-containing crystalline complex, the aluminate [(THF)Li(TMP)(NMe2)Al(Bui)2] has been similarly characterized. All three complexes can be regarded as products of cleave and capture chemistry whereby metallation at the benzylic position of DMPEA has led to a β-elimination of an anionic Me2N fragment that has been captured by a charge balancing cationic heterobimetallic entity. While a metallated intermediate prior to the elimination has proved elusive in all of these reactions, DMPEA has been captured fully intact in the novel Lewis acid–Lewis base crystalline complex [DMPEA·Li(TMP)Zn(Me)2], which has also been characterized by the aforementioned techniques.

AB - Reaction of the sodium monoamido-bisalkylzincate [(TMEDA)Na(TMP)(But)Zn(But)] (TMEDA is N,N,N′,N′-tetramethylethylenediamine; TMP is 2,2,6,6-tetramethylpiperidide) and the related lithium zincate [(PMDETA)Li(TMP)Zn(But)2] (PMDETA is N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) with the sensitive bio-relevant scaffold N,N-dimethylphenylethylamine, DMPEA, afforded the crystalline complexes [(TMEDA)Na(TMP)(NMe2)Zn(But)] and [(PMDETA)Li(NMe2)Zn(But)2], respectively, both of which have been characterized by NMR spectroscopic and X-ray crystallographic studies. Made by reaction of a LiTMP–(TMP)Al(Bui)2 mixture with DMPEA, a third dimethylamino-containing crystalline complex, the aluminate [(THF)Li(TMP)(NMe2)Al(Bui)2] has been similarly characterized. All three complexes can be regarded as products of cleave and capture chemistry whereby metallation at the benzylic position of DMPEA has led to a β-elimination of an anionic Me2N fragment that has been captured by a charge balancing cationic heterobimetallic entity. While a metallated intermediate prior to the elimination has proved elusive in all of these reactions, DMPEA has been captured fully intact in the novel Lewis acid–Lewis base crystalline complex [DMPEA·Li(TMP)Zn(Me)2], which has also been characterized by the aforementioned techniques.

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KW - X-ray crystallography

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SN - 1477-9226

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