NDLI: TMP (2,2,6,6-tetramethylpiperidide)-aluminate bases: lithium-mediated alumination or lithiation

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TMP (2,2,6,6-tetramethylpiperidide)-aluminate bases: lithium-mediated alumination or lithiation–alkylaluminium-trapping reagents?

Content Provider	Royal Society of Chemistry (RSC)
Author	Ramsay, Donna L. Mulvey, Robert E. Crosbie, Elaine Armstrong, David R. Hevia, Eva Robertson, Stuart D.
Copyright Year	2014
Abstract	The lithium TMP-aluminate bases “LiTMP·Al(iBu)3” 1 and “LiTMP·Al(TMP)(iBu)2” 2, where TMP is 2,2,6,6-tetramethylpiperidide, have recently come under the spotlight as “aluminating” reagents in that they can perform aluminium–hydrogen exchange on a wide variety of aromatic substrates. Previous studies have intimated that 1 existed as a single species in THF solution formulated as [(THF)·Li(μ-TMP)(μ-iBu)Al(iBu)2] 1·THF, having a contacted ion pair structure as evidenced by an X-ray crystallographic study of isolated crystals. But here using anisole as a case substrate it is revealed that pre-crystallised 1·THF cannot deprotonate anisole at all whether in hexane or THF solution contradicting earlier in situ applications of 1 which revealed near quantitative metallation of anisole. NMR spectroscopic studies of 1 made in situ in THF solution ascribe this reactivity distinction from 1·THF to complex equilibria involving five major species in LiTMP·THF, Al(iBu)3·THF, [{Li(THF)4}+{Al(TMP)(iBu)3}−] 1·(THF)4, [(THF)·Li(μ-TMP)(μ-OC4H7)Al(iBu)2], 4, and (TMP)Al(iBu)2·THF. Reagent 2 in contrast is found to exist as only two separated homometallic species in LiTMP·THF and (TMP)Al(iBu)2·THF in THF solution. The constitutions of 1 and 2 in non-polar hexane solution are also revealed. With the aid of DFT calculations, discussion focuses on the fact that none of the aluminate species present in THF solutions of 1 or 2 can deprotonate/metallate anisole, instead the metallation processes appear to be LiTMP lithiations followed immediately by trapping by an alkylaluminium complex, in a metal exchange which drives the reaction to the product (arylaluminated) side.
Starting Page	3031
Ending Page	3045
Page Count	15
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	5
Issue Number	8
Journal	Chemical Science
DOI	10.1039/c4sc01108b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	X-ray crystallography THF Metallate TMP Anisole Lithium Ion Hexane Nuclear magnetic resonance spectroscopy Aluminate Li
Content Type	Text
Resource Type	Article
Subject	Chemistry

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Opening the black box of mixed-metal TMP metallating reagents: direct cadmation or lithium–cadmium transmetallation?

The Reactivity of Epoxides with Lithium 2,2,6,6‐Tetramethylpiperidide in Combination with Organolithiums or Grignard Reagents.

Developing a Hetero‐Alkali‐Metal Chemistry of 2,2,6,6‐Tetramethylpiperidide (TMP): Stoichiometric and Structural Diversity within a Series of Lithium/Sodium, Lithium/Potassium and Sodium/Potassium TMP Compounds

cis-2,6-Dimethylpiperidide : a structural mimic for TMP ( 2,2,6,6-tetramethylpiperidide ) or DA ( diisopropylamide )?

Concealed Cyclotrimeric Polymorph of Lithium 2,2,6,6-Tetramethylpiperidide Unconcealed: X-Ray Crystallographic and NMR Spectroscopic Studies

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Mixed Aggregation of Lithium Enolates and Lithium Halides with Lithium 2,2,6,6‐Tetramethylpiperidide (LiTMP).

Macroscopic and microscopic Li⁺ transport parameters in cubic garnet-type “Li_6.5La_2.5Ba_0.5ZrTaO₁₂” as probed by impedance spectroscopy and NMR

TMP (2,2,6,6-tetramethylpiperidide)-aluminate bases: lithium-mediated alumination or lithiation–alkylaluminium-trapping reagents?

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