Axial chirality

Summary

Axial chirality is a special case of chirality in which a molecule does not possess a chiral center (the most common form of chirality in organic compounds) but an axis of chirality, an axis about which a set of substituents is held in a spatial arrangement that is not superposable on its mirror image. Axial chirality is most commonly observed in atropisomeric substituted biaryl compounds wherein the rotation about the aryl–aryl bond is restricted, for example, various biphenyls, binaphthyls such as BINAP, and certain dihydroanthracenone compounds.[1] Certain allene compounds and spirans also display axial chirality. The enantiomers of axially chiral compounds are usually given the stereochemical labels Ra and Sa.[2] The designations are based on the same Cahn–Ingold–Prelog priority rules used for tetrahedral stereocenters. The chiral axis is viewed end-on and the two "near" and two "far" substituents on the axial unit are ranked, but with the additional rule that the two near substituents have higher priority than the far ones.[3]

R and S configurations are determined by precedences of the groups attached to the axial section of the molecule when viewed along that axis.

This property can also be called helicity, since the axis of the structure has a helical, propeller, or screw-shaped geometry. P (plus) or Δ is a right-handed helix, where M (minus) or Λ is a left-handed helix.[4][5] The P/M or Δ/Λ terminology is used particularly for molecules that actually resemble a helix, such as [6]helicene. It can also be applied to other structures having axial chirality by considering the helical orientation of the "front" vs "back" Cahn–Ingold–Prelog rankings.

P helicity
M helicity
Configurations of [7]helicene

External links

  • Axial Chirality in 6,6′-Dinitrobiphenyl-2,2′-dicarboxylic acid 3D representation.

References

  1. ^ Gill, Melvyn; Morgan, Peter M. (2004). "Absolute stereochemistry of fungal metabolites: Icterinoidins A1 and B1, and atrovirins B1 and B2". Arkivoc. 2004 (10): 152–165. doi:10.3998/ark.5550190.0005.a15.
  2. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version:  (2006–) "axial chirality". doi:10.1351/goldbook.A00547
  3. ^ Cross, L. C.; Klyne, W. (1976). "Rules for the Nomenclature of Organic Chemistry. Section E: Stereochemistry (Recommendations 1974)" (PDF). Pure Appl. Chem. 45: 11–30. doi:10.1351/pac197645010011. Chiral axis. The structure is regarded as an elongated tetrahedron and viewed along the axis—it is immaterial from which end it is viewed; the nearer pair of ligands receives the first two positions in the order of preference
  4. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version:  (2006–) "helicity". doi:10.1351/goldbook.H02763
  5. ^ "VLU: Additional Chirality Elements - Chemgapedia". Archived from the original on 2011-07-18. Retrieved 2007-08-06.