Preparation and Cytotoxic Evaluation of Vouacapane Oxidation Products

Talavera-Alemán, Armando; Gómez‐Hurtado, Mario A.; Rodríguez-García, Gabriela; Ochoa‐Zarzosa, Alejandra; Thomassigny, Christine; Cerda-Garcı́a-Rojas, Carlos M.; Joseph‐Nathan, Pedro; Rio, R. E. N. del

doi:10.3987/com-19-14195

Cited by 2 publications

(2 citation statements)

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“…Preliminarily, it was decided to evaluate the synthetic potential of 6 β ‐acetoxyvouacapane by oxidizing the C ring with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) to obtain the benzovouacapane 12 with 60% yield. [ 17 ] Then, it was reacted under Vilsmeier–Haack conditions of 10 with slight modifications to give the novel benzofuran‐aldehyde 13 in 48% yield. Finally, a GBB reaction by using tert ‐butyl isocyanide and 2‐aminopyridine was done, obtaining 14 in a 65% yield (Scheme 4).…”

Section: Resultsmentioning

confidence: 99%

“…[8] On the other hand, the 6β-acetoxyvouacapane 9 is a tetracyclic diterpene isolated from Caesalpinia platyloba with a fused furan ring in its basic polycyclic skeleton, whose chemical transformations, as well as its stereostructure, have been described by del Rio research group. [16][17][18] To our delight, the 6β-acetoxyvouacapane 9 or their derivatives have not been used as starting reagents in multicomponent reactions. Therefore, since there are only two reports describing the use of natural products or their derivatives in the GBB reaction, and in continuation with our research program on the synthesis of biologically relevant compounds via I-MCRs, [19][20][21][22] we describe here a late-stage functionalization of a small series of fused Vouacapane-azoles 11a-f via the GBB reaction (Scheme 1C).…”

Section: Introductionmentioning

confidence: 99%

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Late‐stage functionalization of Vouacapane derivatives from Caesalpinia platyloba by a Groebke−Blackburn−Bienaymé reaction

Servín-García

Chacón-Garcı́a

Islas‐Jácome

et al. 2023

Journal of Heterocyclic Chem

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An almost underexplored field within the natural products area is the synthesis of pseudo‐natural product libraries by employing isocyanide‐based multicomponent reactions as powerful synthetic tools and natural products or their functionalized derivatives as starting reagents. In this work, a novel synthetic strategy behind the late‐stage functionalization of fused Vouacapane‐azoles in a two‐step reaction was developed. The first reaction is a Vilsmeier–Haack formylation at furan ring of the natural product 6β‐acetoxyvouacapane, which was isolated from the leaves of Caesalpinia platyloba from its dichloromethane extracts. The second reaction was a Groebke–Blackburn–Bienaymé reaction to synthesize the pseudo‐natural products 11a‐f in moderate yields, containing pharmacophoric fragments furan and imidazo[1,2‐a]pyridine. The compounds described here are good candidates for biological activity assays.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Late‐stage functionalization of Vouacapane derivatives from Caesalpinia platyloba by a Groebke−Blackburn−Bienaymé reaction

Servín-García

Chacón-Garcı́a

Islas‐Jácome

et al. 2023

Journal of Heterocyclic Chem

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Uncommon Reactivity of a Seco-Oxacassane Diterpenoid and Antiproliferative Activity of Some Derivatives

Torres-Valencia¹,

Hernández-Jiménez²,

De-la-Cruz-Martínez³

et al. 2021

HETEROCYCLES

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The main diterpenoid of Acacia schaffneri, 7,8-seco-7,8-oxacassa-13,15-dien-7-ol-17-al (1), has two aldehydes of which one is protected as a ε-lactol.The free aldehyde resisted to afford the carboxylic acid using reagents with different oxidative strength, although 1 gave oxime 2 when treated with hydroxylamine, β-hydroxyketone 3 after addition of acetone, aldo-ε-lactone 4 whereby only the lactol was oxidized when using Jones reagent, and epoxyformate 5 after Baeyer-Villiger treatment. Hydrolysis of 5 with NaHCO3 gave 6. Structures 2-6 followed from physical and spectral data including X-ray diffraction. All compounds showed antiproliferative activity similar to some chemotherapeutic drugs against C2C12, L929, SiHa, and MDA-MB-231 cell lines. RESULTS AND DISCUSSIONDiterpenoid 1 was obtained in adequate amounts for the preparation of 2-6 from the aerial parts of A.schaffneri. 1 Nucleophilic addition of hydroxylamine to 1 gave 2 in 66% yield, while aldol condensation of 1 with acetone in basic medium led to β-hydroxyketone 3 in 43% yield. The corresponding 1 H NMR spectra did not evidence both syn and anti oximes for 2, nor the absolute configuration (AC) of C-17 in the case of 3. However, the anti oxime geometry in 2 and the (17S) AC in 3 followed from the X-ray diffraction (XRD) studies detailed below. Although 3 was not the only expected condensation product, the γ,δ-unsaturated carbonyl compound could not be obtained even when using large excesses of acetone and NaOH.

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Preparation and Cytotoxic Evaluation of Vouacapane Oxidation Products

Cited by 2 publications

References 41 publications

Late‐stage functionalization of Vouacapane derivatives from Caesalpinia platyloba by a Groebke−Blackburn−Bienaymé reaction

Late‐stage functionalization of Vouacapane derivatives from Caesalpinia platyloba by a Groebke−Blackburn−Bienaymé reaction

Uncommon Reactivity of a Seco-Oxacassane Diterpenoid and Antiproliferative Activity of Some Derivatives

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