Chiral action at a distance: remote substituent effects on the optical activity of calyculins A and B.

Journal Article (Journal Article)

[structure--see text] Calyculins A and B differ only by the (E)- vs (Z)-configuration at C(2). Yet, they show a large difference in optical rotations. We demonstrate a new strategy that provides a physical analysis of this long-range chiro-optical effect by Boltzmann-averaged atomic contribution mapping. The polarizability characteristics of the CN substituent rather than the perturbation of the stereogenic centers or the introduction of asymmetry into the polyene chain give rise to the remarkable difference in rotation angles.

Full Text

Duke Authors

Cited Authors

  • Kondru, RK; Beratan, DN; Friestad, GK; Smith, AB; Wipf, P

Published Date

  • June 2000

Published In

Volume / Issue

  • 2 / 11

Start / End Page

  • 1509 - 1512

PubMed ID

  • 10841466

Electronic International Standard Serial Number (EISSN)

  • 1523-7052

International Standard Serial Number (ISSN)

  • 1523-7060

Digital Object Identifier (DOI)

  • 10.1021/ol005634p


  • eng