Vanadium haloperoxidase-catalyzed bromination and cyclization of terpenes.
Marine red algae (Rhodophyta) are a rich source of bioactive halogenated natural products, including cyclic terpenes. The biogenesis of certain cyclic halogenated marine natural products is thought to involve marine haloperoxidase enzymes. Evidence is presented that vanadium bromoperoxidase (V-BrPO) isolated and cloned from marine red algae that produce halogenated compounds (e.g., Plocamium cartilagineum, Laurencia pacifica, Corallina officinalis) can catalyze the bromination and cyclization of terpenes and terpene analogues. The V-BrPO-catalyzed reaction with the monoterpene nerol in the presence of bromide ion and hydrogen peroxide produces a monobromo eight-membered cyclic ether similar to laurencin, a brominated C15 acetogenin, from Laurencia glandulifera, along with noncyclic bromohydrin, epoxide, and dibromoproducts; however, reaction of aqueous bromine with nerol produced only noncyclic bromohydrin, epoxide, and dibromoproducts. The V-BrPO-catalyzed reaction with geraniol in the presence of bromide ion and hydrogen peroxide produces two singly brominated six-membered cyclic products, analogous to the ring structures of alpha and beta snyderols, brominated sesquiterpenes from Laurencia, spp., along with noncyclic bromohydrin, epoxide, and dibromoproducts; again, reaction of geraniol with aqueous bromine produces only noncyclic bromohydrin, epoxide, and dibromoproducts. Thus, V-BrPO can direct the electrophilic bromination and cyclization of terpenes.
Carter-Franklin
Jayme N
JN
Department of Chemistry and Biochemistry, University of California, Santa Barbara 93106-9510, USA.
Parrish
Jon D
JD
Tschirret-Guth
Richard A
RA
Little
R Daniel
RD
Butler
Alison
A
D002384:Catalysis; D003500:Cyclization; D006842:Hydrocarbons, Brominated / Q000138:chemical synthesis* / Q000378:metabolism; D010544:Peroxidases / Q000737:chemistry* / Q000378:metabolism; D000461:Rhodophyta / Q000201:enzymology; D013729:Terpenes / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism
D006842:Hydrocarbons, Brominated; D013729:Terpenes; D010544:Peroxidases; C026195:bromide peroxidase