Controlling helical chirality in atrane structures: solvent-dependent chirality sense in hemicryptophane-oxidovanadium(V) complexes

Chemistry : a European Journal
Alexandre MartinezJean-Pierre Dutasta

Abstract

The diastereomeric hemicryptophane oxidovanadium(V) complexes (P)-(S,S,S)-3 and (M)-(S,S,S)-4 have been synthesized. (1)H and (51)V NMR spectra in solution are consistent with the formation of Lambda and Delta forms of the propeller-like vanatrane moiety, leading to two diastereomeric conformers for each complex: that is, (P)-(S,S,S-Lambda)-3/(P)-(S,S,S-Delta)-3 and (M)-(S,S,S-Lambda)-4/(M)-(S,S,S-Delta)-4. The Lambda/Delta ratio is rather temperature-insensitive but strongly dependent on the solvent (the de of (M)-(S,S,S)-4 changes from 0 in benzene to 92 % in DMSO). The solvent therefore controls the preferential clockwise or anticlockwise orientation of the propeller-like atrane unit. The energy barriers for the Lambdaright arrow over left arrowDelta equilibrium were determined by NMR experiments, and the highest DeltaG( not equal) value (103.7 kJ mol(-1)) was obtained for (P)-(S,S,S)-3, much higher than those reported for other atrane derivatives. This is attributed to the constraints arising from the cage structure. Determination of the activation parameters provides evidence for a concerted, rather than a stepwise, interconversion mechanism with entropies (DeltaS( not equal)) of -243 and -272 J mol(-1) K(-1) for (P)-(S,S,...Continue Reading

References

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Citations

Jan 29, 2011·The Journal of Organic Chemistry·Najat S KhanIvan J Dmochowski
Jan 16, 2016·Inorganic Chemistry·Isabelle GosseJean-Pierre Dutasta
Dec 24, 2014·Organic & Biomolecular Chemistry·Aline SchmittAlexandre Martinez
Jan 11, 2016·Chemistry : a European Journal·Sara LefevreAlexandre Martinez
Mar 5, 2014·Chemistry : a European Journal·James J HenkelisMichaele J Hardie
Jun 1, 2011·Chemistry : a European Journal·Christina Tepper, Gebhard Haberhauer
Oct 21, 2011·Chemistry : a European Journal·Olivier PerraudJean-Pierre Dutasta
Jan 9, 2013·Chemical Communications : Chem Comm·Olivier PerraudAlexandre Martinez
May 20, 2014·Organic & Biomolecular Chemistry·Aline SchmittAlexandre Martinez
Nov 10, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Olivier PerraudAlexandre Martinez
Dec 14, 2011·Organic & Biomolecular Chemistry·Olivier PerraudJean-Pierre Dutasta
Mar 8, 2011·Chemistry : a European Journal·Olivier PerraudJean-Pierre Dutasta
Feb 20, 2010·The Journal of Organic Chemistry·Pascal Dimitrov RaytchevJean-Pierre Dutasta
Jun 12, 2010·Journal of the American Chemical Society·Alexandre MartinezJean-Pierre Dutasta
Feb 2, 2011·Journal of the American Chemical Society·Pascal Dimitrov RaytchevJean-Pierre Dutasta
Jun 15, 2011·Organic Letters·Bastien ChateletJean-Pierre Dutasta
Oct 2, 2021·The Journal of Organic Chemistry·Chunyang LiAlexandre Martinez

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