Enzymelike catalysis of the Nazarov cyclization by supramolecular encapsulation.
The water-soluble, self-assembled, tetrahedral assembly K(12)Ga(4)L(6) (L = 1,5-biscatecholamidenaphthalene) catalyzes the Nazarov cyclization of 1,3-pentadienols with extremely high levels of efficiency. The catalyzed reaction proceeds over a million times faster than the background reaction, an increase comparable to those observed in some enzymatic systems. This catalysis operates under aqueous conditions at mild temperatures and pH, and the reaction is halted by the addition of an appropriate inhibitor. This unprecedented rate enhancement is attributed to both the stabilization of protonated reaction intermediates and the effect of constrictive binding on the bound guest.
Hastings
Courtney J
CJ
Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
Pluth
Michael D
MD
Bergman
Robert G
RG
Raymond
Kenneth N
KN
D000438:Alcohols / Q000737:chemistry; D032701:Biomimetics; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D004798:Enzymes / Q000737:chemistry / Q000378:metabolism*; D007700:Kinetics; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D013696:Temperature
D000438:Alcohols; D004798:Enzymes; D008024:Ligands; D002244:Carbon