Abstract

alpha-Lithiated epoxides, long considered "fleeting" intermediates in the reactions of epoxides with strong bases, have nowadays proven to be key synthons for asymmetric synthesis. In this study, the solution and the solid state structure of an alpha-lithiated aryloxirane, namely a-lithiated ortho-trifluoromethyl styrene oxide (1-Li), were determined. Single crystal X-ray diffraction analysis of 1-Li performed at 100 K applying the X-TEMP-2 device revealed a self-assembled heterochiral dimeric structure with a rare central six-membered (O-Li-C)(2) planar core, which is unprecedented in Li/oxygen carbenoids. Multinuclear magnetic resonance (H-1, C-13, F-19, Li-7) studies suggested that 1-Li exists in THF solution as a mixture of two interconverting diastereomeric dimeric aggregates, each one featuring a single s-contact between lithium and a carbon atom. Line shape analysis provided activation parameters for both the dynamic interconversion of the two dimers and the enantiomerisation of 1-Li, which proved to be mostly entropy controlled. The structural assignment in solution was supported by density functional theory computations through the investigation of conformers of monomeric and dimeric complexes of 1-Li featuring different degrees of specific solvation. A mechanism based on the equilibration of six-membered homo-and heterochiral dimers was proposed to explain the configurational instability exhibited by 1-Li in THF.

Autore Pugliese

• Moliterni Anna , Falcicchio Aurelia

Tutti gli autori

• Salomone A.; Perna F.M.; Falcicchio A.; Nilsson Lill S.O. ; Moliterni A.; Michel R.; Florio S.; Stalke D.; Capriati V.

Titolo volume/Rivista

Chemical science

Anno di pubblicazione

2014

ISSN

2041-6520

ISBN

Non Disponibile

Numero di citazioni Wos

Nessuna citazione

Ultimo Aggiornamento Citazioni

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Numero di citazioni Scopus

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Ultimo Aggiornamento Citazioni

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Settori ERC

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Codici ASJC

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