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PMID: 19199623 Published · ppublish English Journal Article Research Support, N.I.H., Extramural Research Support, Non-U.S. Gov't

Cascade reactions during coronafacic acid biosynthesis: elongation, cyclization, and functionalization during Cfa7-catalyzed condensation.

Journal of the American Chemical Society ·Vol. 131 ·No. 6 ·2009-02-18 ·Pages 2113-5

Strieter ER, Koglin A, Aron ZD, Walsh CT

Abstract

Herein, the biogenesis of the hydrindane ring system within coronafacic acid (CFA) has been investigated. These studies reveal that in addition to the canonical polyketide chain elongation and functionalization encoded by type I polyketide synthase (PKSs), cascade reactions can take place during assembly line-like biosynthesis. Indeed, upon Cfa7-catalyzed Claisen condensation between enzyme-bound malonate and an N-acetylcysteamine (SNAC) thioester, latent reactivity within the elongated enzyme-bound intermediate is unveiled. This reactivity translates into an intramolecular cyclization, which can proceed in a facile manner as observed by the enzyme-independent cyclization of a linear beta-ketothioester intermediate.

MeSH Terms
Catalysis Cyclization Cysteamine/analogs & derivatives,metabolism Indenes/metabolism Malonates/metabolism Polyketide Synthases/metabolism Pseudomonas putida/enzymology,metabolism
Chemicals
Indenes Malonates Cysteamine coronafacic acid Polyketide Synthases malonic acid
Authors & Affiliations
4 authors, click to expand affiliations / ORCID
Strieter Eric R
Harvard Medical School, Department of Biological Chemistry and Molecular Pharmacology, 240 Longwood Avenue, Boston, Massachusetts 02115, USA.
Koglin Alexander
Aron Zachary D
Walsh Christopher T
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Article Info
Journal
Journal of the American Chemical Society
Abbr.
J Am Chem Soc
ISSN
1520-5126
DOI
10.1021/ja8077945
Published
2009-02-18
Pages
2113-5
Language
English
Region
United States
NLM ID
7503056
PMCID
PMC2662718
Subset
IM
Grants
NIGMS NIH HHS · F32 GM020011 · United States
NIGMS NIH HHS · F32 NRSA GM7229-01 · United States
NIGMS NIH HHS · GM20011 · United States
NIGMS NIH HHS · T32 GM007229 · United States
NIGMS NIH HHS · R01 GM020011-38 · United States
NIGMS NIH HHS · R01 GM020011 · United States
External Links
PubMed source DOI: 10.1021/ja8077945 PMC Full Text View journal details
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