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Direct observation of a lithiated oxirane: A synergistic study using spectroscopic, crystallographic, and theoretical methods on the structure and stereodynamics of lithiated ortho-trifluoromethyl styrene oxide

Författare och institution:
A. Salomone (-); F. M. Perna (-); A. Falcicchio (-); Sten O. Nilsson Lill (Institutionen för kemi och molekylärbiologi); A. Moliterni (-); R. Michel (-); S. Florio (-); D. Stalke (-); V. Capriati (-)
Publicerad i:
CHEMICAL SCIENCE, 5 ( 2 ) s. 528-538
Artikel, refereegranskad vetenskaplig
Sammanfattning (abstract):
α-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 α-lithiated aryloxirane, namely α-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 ( 1H, 13C, 19F, 7Li) studies suggested that 1-Li exists in THF solution as a mixture of two interconverting diastereomeric dimeric aggregates, each one featuring a single σ-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. © 2014 The Royal Society of Chemistry.
Ämne (baseras på Högskoleverkets indelning av forskningsämnen):
Activation parameter, Asymmetric synthesis, Direct observations, Multinuclear magnetic resonance, Single crystal X-ray diffraction analysis, Solid-state structures, Structural assignments, Theoretical methods, Dimers, Magnetic resonance, Reaction intermediates, Single crystals, Styrene, X ray diffraction analysis, Lithium
Postens nummer:
Posten skapad:
2014-03-18 11:03
Posten ändrad:
2014-12-10 13:19

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