Synthetic studies towards naturally occurring γ-(<i>Z</i>)/(<i>E</i>)-alkylidenebutenolides through bimetallic cascade cyclization and an adventitious photoisomerization method

Nanda, Samik; Chatterjee, Shrestha; Acharyya, Ranjan Kumar; Pal, Pratik

doi:10.1039/d2ob00166g

Cited by 5 publications

(9 citation statements)

References 78 publications

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“…13 C NMR (150 MHz, CDCl 3 ): δ 169.3 (C-1), 157.7 (C-4), 140.5 (C-3), 121.1 (C-2), 100.8 (C-6), 96.2 (C-5), 74.5 (C-7), 22.1 (C-8), 22.0 (C-9), 13.7 (C-10). EI-MS m/z (%): 162 (M + , 84), 147 (19), 133 (36), 105 (32), 91 (29) 26,34 Unreacted starting material 1 was recovered (50 mg, 50% yield, R f = 0.3 petroleum ether/EtOAc 9/1 v/v) during the flash chromatographic purification procedure.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…In the design of a synthetic approach toward (4 Z )-lachnophyllum lactone ( 1 ), our work started with the construction of a possible retrosynthetic pathway analysis (Scheme ). The key step identified was based on a Pd–Cu bimetallic cascade cross-coupling cyclization , procedure, between 3- Z -iodoacrylic acid (Scheme , blue) and 1,3-eptadiyne (Scheme , green). These coupling partners can be easily prepared from commercially available precursors, such as propiolic acid and 1-pentyne correspondingly (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

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(4Z)-Lachnophyllum Lactone, a Metabolite with Phytotoxic and Antifungal Activity against Pests Affecting Mediterranean Agriculture: A New Versatile and Easy Scalable Parallel Synthesis

Soriano,

Arnodo,

Masi

et al. 2024

J. Agric. Food Chem.

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A methodology for the total and modulable synthesis of (4Z)-lachnophyllum lactone (1), on a gram scale, is reported for the first time. The present work started with the design of a retrosynthetic pathway for the target compound, with the key step identified in Pd−Cu bimetallic cascade cross-coupling cyclization. (4Z)-Lachnophyllum lactone (1) is an acetylenic furanone previously isolated, in a low amount, from the organic extract of the autotrophic weedConyza bonariensis. Tested against the stem parasitic weed Cuscuta campestris in a seedling growth bioassay, (4Z)-lachnophyllum lactone (1) showed almost 85% of inhibitory activity up to 0.3 mM in comparison with the control. At the same concentration, the compound displayed radicle growth inhibitory activity of the root parasitic weeds Orobanche minor and Phelipanche ramosa higher than 70 and 40%, respectively. Surprisingly, the compound showed a high percentage of inhibition, up to 0.1 mM, on C. bonariensis seed germination too. This versatile synthetic strategy was also used to obtain two further natural analogues, namely, (4E)-lachnophyllum lactone ( 8) and (4Z,8Z)-matricaria lactone (9), that showed, in most cases, the same inhibitory trend with slight differences, highlighting the importance of the stereochemistry and unsaturation of the side chain. Furthermore, all of the compounds showed antifungal activity at 1 mM reducing the mycelial growth of the olive pathogen Verticillium dahliae. The design and implementation of scalable and modulable total synthesis on a gram scale of acetylenic furanones allow the production of a large amount of these natural products, overcoming the limit imposed by isolation from natural sources. The results of the present study pave the way for the development of ecofriendly bioinspired pesticides with potential application in agrochemical practices as alternative to synthetic pesticides.

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Section: ■ Materials and Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

(4Z)-Lachnophyllum Lactone, a Metabolite with Phytotoxic and Antifungal Activity against Pests Affecting Mediterranean Agriculture: A New Versatile and Easy Scalable Parallel Synthesis

Soriano,

Arnodo,

Masi

et al. 2024

J. Agric. Food Chem.

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“…For the preparation of the third building block, methyl d -lactate ( 13 ) was O-silylated and the resulting ester reduced with DIBAL-H; lithiated TMS-acetylene was then added to the aldehyde thus formed. This reaction was diastereoselective ( anti / syn ≈ 8:1), high yielding, and scalable . Orthogonal protection of the newly formed alcohol in 14 followed by cleavage of the C-TMS group gave 15 .…”

mentioning

confidence: 92%

“…This reaction was diastereoselective (anti/syn ≈ 8:1), high yielding, and scalable. 33 protection of the newly formed alcohol in 14 followed by cleavage of the C-TMS group gave 15. Attempted carboalumination 15 (or partly deprotected analogues) followed by an iodine quench basically met with failure; gratifyingly though, a copper catalyzed net carboboration constituted a convenient and robust alternative that provided access to 16 in good yield and excellent selectivity.…”

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confidence: 99%

Total Synthesis of the Allenic Macrolide (+)-Archangiumide

Sutro,

Fürstner

2024

J. Am. Chem. Soc.

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Archangiumide is the first known macrolide natural product comprising an endocyclic allene. For the ring strain that this linear substructure might entail, it was planned to unveil the allene at a very late stage of the projected total synthesis; in actual fact, this was achieved as the last step of the longest linear sequence by using an otherwise globally deprotected substrate. This unconventional timing was made possible by a gold catalyzed rearrangement of a macrocyclic propargyl benzyl ether derivative that uses a −PMB group as latent hydride source to unveil the signature cycloallene; the protecting group therefore gains a strategic role beyond its mere safeguarding function. Although the gold catalyzed reaction per se is stereoablative, the macrocyclic frame of the target was found to impose high selectivity and a stereoconvergent character on the transformation. The required substrate was formed by ring closing alkyne metathesis (RCAM) with the aid of a new air-stable molybdenum alkylidyne catalyst.

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“…The secondary 1,3‐dienyl‐5‐ester is a commonly encountered motifs in natural products and biologically active molecules (Scheme 1a), selected examples such as anguinomycins C/D, [1] acetylmelodorinol, [2] reveromycin B [3] and zooxanthellactone [4] and so on. Moreover, 1,3‐dienes are also a versatile synthetic intermediate for constructing bioactive molecules and natural product [5] .…”

Section: Introductionmentioning

confidence: 99%

Iridium‐Catalyzed C5‐Regioselective Esterification of Dienyl Alcohols with Carboxylic Acids

et al. 2023

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One‐step process for the preparation of a 1,3‐dienyl‐5‐ester motif from readily available substrate remains a challenging work in organic synthesis. We herein report the first example of C5‐regioselective esterification of unactivated dienyl alcohols, using free carboxylic acids as nucleophiles under mild conditions, providing a series of 1,3‐dienyl‐5‐ester compounds in excellent regioselectivity and E‐selectivity.

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Synthetic studies towards naturally occurring γ-(Z)/(E)-alkylidenebutenolides through bimetallic cascade cyclization and an adventitious photoisomerization method

Abstract: A general and flexible visible light-induced photoisomerization method of γ-(Z)-alkylidenebutenolides to its corresponding E-components was reported in this article. Initially, a series of naturally occurring enantiopure γ-(Z)-alkylidenebutenolides was synthesized by...

Cited by 5 publications

References 78 publications

(4Z)-Lachnophyllum Lactone, a Metabolite with Phytotoxic and Antifungal Activity against Pests Affecting Mediterranean Agriculture: A New Versatile and Easy Scalable Parallel Synthesis

(4Z)-Lachnophyllum Lactone, a Metabolite with Phytotoxic and Antifungal Activity against Pests Affecting Mediterranean Agriculture: A New Versatile and Easy Scalable Parallel Synthesis

Total Synthesis of the Allenic Macrolide (+)-Archangiumide

Iridium‐Catalyzed C5‐Regioselective Esterification of Dienyl Alcohols with Carboxylic Acids

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