Synthesis and properties of trans-3-(1,4-cyclohexadienyl)acrylic acid

Ressler, Charlotte; Goodman, Francis J.; Tsutsui, Ryoki; Tsutsumi, Masahiro; Hanson, Kenneth R.

doi:10.1021/jo01326a030

Cited by 4 publications

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References 2 publications

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“…[1,2- 13 C 2 ]- 5 was synthesized in 43.3% overall yield from 4-methoxybenzaldehyde by nitration with NH 4 NO 3 /trifluoroacetic anhydride (TFAA) to 3-nitro-4-methoxybenzaldehyde, followed by a Knoevenagel condensation with [U- 13 C 3 ]malonic acid, demethylation with LiI,and reduction of the nitro group with SnCl 2 (Scheme 2A). Preparation of the corresponding N -acetylcysteamine (SNAC) thioester 5a proved problematic because of interference of the phenolic hydroxy group and failure of common protecting groups (e.g., TBDMS, Boc), but was finally accomplished in poor yield (15%) by direct esterification of 5 with N -acetylcysteamine catalyzed by DCC and DMAP .…”

Section: Resultsmentioning

confidence: 99%

Further Studies on the Biosynthesis of the Manumycin-Type Antibiotic, Asukamycin, and the Chemical Synthesis of Protoasukamycin

Floss

2004

J. Am. Chem. Soc.

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Asukamycin (2), a metabolite of Streptomyces nodosus ssp. asukaensis ATCC 29757 and a member of the manumycin family of antibiotics, is assembled from three components, an "upper" polyketide chain initiated by cyclohexanecarboxylic acid, a "lower" polyketide chain initiated by the novel starter unit, 3-amino-4-hydroxybenzoic acid (3,4-AHBA), and a cyclized 5-aminolevulinic acid moiety, 2-amino-3-hydroxycyclopent-2-enone (C(5)N unit). To shed light on the order in which these components are assembled, we synthesized in labeled form various potential intermediates and evaluated their incorporation into 2. The assembly of the molecular framework of 2 from 3,4-AHBA and cyclohexanecarboxylic acid apparently does not involve free, unactivated intermediates. However, protoasukamycin (12), the total synthesis of which is reported, was efficiently converted into 2, demonstrating that the modification of the aromatic ring to the epoxyquinol structure is the terminal step in the biosynthesis. The results suggest that the two polyketide chains are synthesized separately and that the "upper" chain must be connected to the "lower" polyketide chain before the C(5)N unit.

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Section: Resultsmentioning

confidence: 99%

Further Studies on the Biosynthesis of the Manumycin-Type Antibiotic, Asukamycin, and the Chemical Synthesis of Protoasukamycin

Floss

2004

J. Am. Chem. Soc.

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“…The structure of the product is established to be irans-3-(l,4-cyclohexadienyl)acrylic acid, 4, on the basis of its mode of formation, its NMR and UV spectra, its p£a value, and its identity with the compound obtained by chemical synthesis. The identity has been established by melting point, and by UV, IR, and NMR spectroscopy comparisons (Ressler et al, 1979).…”

Section: Resultsmentioning

confidence: 99%

“…A low intensity signal at 7.5 in the NMR spectrum of this material is attributable to a phenyl ring and indicates the presence of cinnamic acid (<4%) as a contaminant. The peak was not observed in the spectrum of synthetic material purified by LC (Ressler et al, 1979). The same material examined over a year later by LC contained -6% cinnamic acid.…”

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confidence: 87%

“…The kinetic results are discussed in relation to the biosynthesis of compounds structurally related to sorbic acid and to the mechanism of the elimination reaction. A subsequent paper will describe the chemical synthesis of the dihydro acid 4 and its biological activity (Ressler et al, 1979).…”

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confidence: 99%

“…ration can be achieved by zone electrophoresis on paper, by partition chromatography on buffered silica gel columns, and also by LC (Ressler et al, 1979).…”

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confidence: 99%

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Phenylalanine ammonia-lyase: enzymic conversion of 3-(1,4-cyclohexadienyl)-L-alanine to trans-3-(1,4-cyclohexadienyl)acrylic acid

Hanson¹,

Havir²,

Ressler³

1979

Biochemistry

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The phenylalanine analogue 3-(1,4-cyclohexadienyl)-L-alanine is converted to the hitherto unknown cinnamate analogue trans-3-(1,4-cyclohexadienyl)acrylic acid by L-phenylalanine ammonia-lyase (EC 4.3.1.5) from maize, potato, or Rhodotorula glutinis. The structure assigned to the product is confirmed by its 1H nuclear magnetic resonance spectrum and by the chemical synthesis to be described in a subsequent paper. On comparing the above substrate analogue with L-phenylalanine, the Km was lowered only slightly but kcat was reduced 14--40-fold depending on the source of the enzyme. Because the compounds closely resemble each other in size and hydrophobic properties, this lowering of kcat may be attributed to the electronic effect of replacing the pi electrons of the aromatic system by those of a double bond. Correct alignment at the active site appears to depend upon the space-filling properties of the ring system; open chain analogues that retain the gamma, beta double bond were found to be inhibitors, not substrates.

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ChemInform Abstract: SYNTHESIS AND PROPERTIES OF TRANS‐3‐(1,4‐CYCLOHEXADIENYL)ACRYLIC ACID

Ressler¹,

Goodman²,

Tsutsui³

et al. 1979

Chemischer Informationsdienst

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Synthesis and properties of trans-3-(1,4-cyclohexadienyl)acrylic acid

Cited by 4 publications

References 2 publications

Further Studies on the Biosynthesis of the Manumycin-Type Antibiotic, Asukamycin, and the Chemical Synthesis of Protoasukamycin

Further Studies on the Biosynthesis of the Manumycin-Type Antibiotic, Asukamycin, and the Chemical Synthesis of Protoasukamycin

Phenylalanine ammonia-lyase: enzymic conversion of 3-(1,4-cyclohexadienyl)-L-alanine to trans-3-(1,4-cyclohexadienyl)acrylic acid

ChemInform Abstract: SYNTHESIS AND PROPERTIES OF TRANS‐3‐(1,4‐CYCLOHEXADIENYL)ACRYLIC ACID

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