Chiral action at a distance: remote substituent effects on the optical activity of calyculins A and B.
[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.
Kondru
R K
RK
Department of Chemistry, University of Pittsburgh, Pennsylvania 15260, USA.
Beratan
D N
DN
Friestad
G K
GK
Smith
A B
AB
Wipf
P
P
D001685:Biological Factors / Q000737:chemistry; D002273:Carcinogens / Q000737:chemistry; D004791:Enzyme Inhibitors / Q000737:chemistry; D008387:Marine Toxins; D008958:Models, Molecular; D008968:Molecular Conformation; D009904:Optical Rotation; D010755:Organophosphates / Q000737:chemistry*; D010080:Oxazoles / Q000737:chemistry*; D010749:Phosphoprotein Phosphatases / Q000037:antagonists & inhibitors; D013237:Stereoisomerism; D013816:Thermodynamics; D014662:Vasoconstrictor Agents / Q000737:chemistry
D001685:Biological Factors; D002273:Carcinogens; D004791:Enzyme Inhibitors; D008387:Marine Toxins; D010755:Organophosphates; D010080:Oxazoles; D014662:Vasoconstrictor Agents; C410202:calyculin B; C059041:calyculin A; D010749:Phosphoprotein Phosphatases