10.1021/jo0267596.s001
Hideaki Oikawa
Hideaki
Oikawa
Biosynthesis of Structurally Unique Fungal Metabolite
GKK1032A<sub>2</sub>: Indication of Novel Carbocyclic Formation
Mechanism in Polyketide Biosynthesis
American Chemical Society
2003
polyketide chain
nonribosomal peptide synthetase
Novel Carbocyclic Formation Mechanism
oxidation level
GKK 1032.
antitumor agent GKK 1032A 2
biosynthesi
macroether
nonaketide chain
novel cyclization mechanisms
starter unit
13 C
tyrosine hydroxy group
Penicillium sp
methyl groups
polyketide synthase
Polyketide Biosynthesis
2 H
tricarbocyclic system
formation
2003-03-28 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Biosynthesis_of_Structurally_Unique_Fungal_Metabolite_GKK1032A_sub_2_sub_Indication_of_Novel_Carbocyclic_Formation_Mechanism_in_Polyketide_Biosynthesis/3697590
The biosynthesis of the antitumor agent GKK1032A<sub>2</sub> (<b>1) </b>has been investigated by administration
of isotopically labeled (<sup>13</sup>C and <sup>2</sup>H) precursors to <i>Penicillium</i> sp. GKK1032. These studies showed
that the backbone of <b>1</b> is constructed from l-tyrosine and a nonaketide chain flanked with five
methyl groups probably by a polyketide synthase and a nonribosomal peptide synthetase hybrid.
On the basis of the oxidation level of the starter unit and unusual 13-membered macroether
formation between the tyrosine hydroxy group and the polyketide chain, novel cyclization
mechanisms on the formation of a tricarbocyclic system and a macroether have been proposed.
Involvement of a similar type of cyclization in the biosynthesis of structurally related metabolites
is discussed.