2007
DOI: 10.1021/ja0736919
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A New Mechanism for Benzopyrone Formation in Aromatic Polyketide Biosynthesis

Abstract: Aromatic polyketides are all biosynthesized from highly reactive poly-β-ketone intermediates. Keys to introducing the vast chemical diversity seen in these natural products are the enzymatic and non-enzymatic tailoring chemistries that occur after biosynthesis of the poly-β-keto backbone. In this work, we expand the scope of non-enzyme-catalyzed modifications and show that primary amides can act in vivo as an electrophilic center and be attacked by an intramolecular phenol to generate dibenzopyrones. Synthetic… Show more

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Cited by 38 publications
(23 citation statements)
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“…We first constructed a pSET152-derived integrating vector57 containing ssfY1 and cotransformed the resulting plasmid pLP77 with pLP27 into K4-114. We detected the complete disappearance of 42 in the extract and emergence of a single major product that corresponds to the benzopyrone WJ78 44 (Figure 5B), which is the shunt product of the amidated polyketide intermediate 43 that has been regioselectively cyclized at the D-ring58. Cotransformation of K4-114 with pLP27 and an integrating vector containing s sfY3 , did not lead to the recovery of 44 , indicating SsfY3 cannot substitute for SsfY1 and likely serves a different role in the biosynthesis of 1 .…”
Section: Resultsmentioning
confidence: 99%
“…We first constructed a pSET152-derived integrating vector57 containing ssfY1 and cotransformed the resulting plasmid pLP77 with pLP27 into K4-114. We detected the complete disappearance of 42 in the extract and emergence of a single major product that corresponds to the benzopyrone WJ78 44 (Figure 5B), which is the shunt product of the amidated polyketide intermediate 43 that has been regioselectively cyclized at the D-ring58. Cotransformation of K4-114 with pLP27 and an integrating vector containing s sfY3 , did not lead to the recovery of 44 , indicating SsfY3 cannot substitute for SsfY1 and likely serves a different role in the biosynthesis of 1 .…”
Section: Resultsmentioning
confidence: 99%
“…Palladium catalyzed Stille coupling of 5 with the readily available trimethyl (2-nitrophenyl) stannane [47] afforded 6 in 83% yield. Similarly, this key nitro intermediate can also be prepared by the Suzuki coupling of bromide 7 and 2-nitrophenyl boronic acid [33,48] (Scheme 3).…”
Section: Resultsmentioning
confidence: 99%
“…[13] To induce this characteristic feature of natural products in our collection of tricyclic benzopyrones, 3-formyl-5-hydroxychromone (1 c) and the methyl derivative (1 b) were synthesized by the Vilsmeier-Haack reaction of the corresponding hydroxyacetophenones, according to literature procedures (see the Supporting Information). [14] In addition, 3-formylbenzo[h]chromone with a bulky naphthalene ring (1 d) was employed in the annulation reactions with acetylenes.…”
Section: Resultsmentioning
confidence: 99%
“…After evaporation of the solvent, the crude product was purified by column chromatography (silica gel, CH/EtOAc 9:1) to yield dihydropyridine 18 a and pyridine 19 a. 1, 162.8, 162.0, 156.9, 155.6, 152.9, 144.9, 134.9, 133.7, 129.2, 127.8, 125.3, 125.1, 124.1, 118.0, 116.1, 115.4, 60.0, 56.9, 51.9, 21.4 197.4, 166.1, 164.8, 163.6, 153.0, 151.5, 138.3, 137.8, 134.7, 132.9, 126.1, 119.6, 119.2, 118.8, 53.5, 53.4 1, 156.7, 155.6, 152.7, 144.9, 135.0, 133.7, 129.2, 127.9, 125.4, 125.1, 124.1, 118.0, 117.1, 115.8, 68.6, 60.9, 56.8, 21.4, 15.6, 13.9 197.6, 164.4, 163.6, 153.5, 151.4, 138.3, 137.8, 134.5, 132.9, 126.2, 119.6, 119.1, 77.5, 77.2, 76.8, 62.8, 62.7, 14.2 (s,1 H),J = 8.4,2.0 Hz,2 H),7.52 (d,J = 0.8 Hz,1 H),J = 8.4,2.0 Hz,1 H),J = 8.4 Hz,1 H),J = 8.4 Hz,2 H),5.48 (s,1 H),4.33 (s,3 H),3.69 (s,3 H),2.38 (s,3 H), 2.17 ppm (s, 3 H); 13 C NMR (100 MHz, CDCl 3 ): d = 175. 2, 162.9, 162.1, 156.9, 153.9, 152.9, 144.9, 135.3, 135.0, 134.9, 129.2, 127.8, 124.7, 123.8, 117.7, 116.2, 115.1, 60.0, 56.9, 51.9, 21.3, 20.8 197.3, 166.2, 164.9, 161.6, 152.9, 151.4, 139.0, 138.2, 134.9, 132.4, 128.9, 126.2, 118.9, 118.5, 53.5, 53.4, 20.6 J = 8.4,2.0 Hz,2 H),J = 1.2,0.4 Hz,1 H),J = 8.4,2.4,0.4 Hz,1 H),J = 8.4 Hz,1 H),…”
Section: N [M+h]mentioning
confidence: 99%