Convenient synthesis of α,β-unsaturated γ-butyrolactones and γ-butyrolactams via decarboxylative iodination of paraconic acids and β-carboxyl-γ-butyrolactams using 1,3-diiodo-5,5-dimethylhydantoin

Phae-nok, Supasorn; Kuhakarn, Chutima; Pohmakotr, Manat; Reutrakul, Vichai; Soorukram, Darunee

doi:10.1039/c5ob01574j

Cited by 10 publications

(4 citation statements)

References 88 publications

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“…For example, Spirofragilide is a sesquiterpene that is isolated from marine sponge Dysidea fraglis, possesses antitumor, anti-inflammatory, antibiotic, and anti-HIV activities. [15] Stypolactone is a diterpenoid isolated from brown alga, Stypodium zonalethat contains spirobutenolide as a sub-structure. [16] Two pigments, hydnuferruginin and hydnuferrugin [17] have been isolated from the sporophores of fungi Hydnellumferrugineum and H. zonatum.…”

Section: Important Natural Products Containing Spiro δ à Butenolides mentioning

confidence: 99%

“…The presence of Δ α , β ‐ and Δ β , γ ‐butenolides as subunits in different naturally occurring biologically active spirobutenolides are primarily responsible for pharmacological responses and have acquired unique place. For example, Spirofragilide is a sesquiterpene that is isolated from marine sponge Dysidea fraglis , possesses antitumor, anti‐inflammatory, antibiotic, and anti‐HIV activities . Stypolactone is a diterpenoid isolated from brown alga, Stypodium zonale that contains spirobutenolide as a sub‐structure .…”

Section: Important Natural Products Containing Spiro δ−Butenolides Anmentioning

confidence: 99%

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Natural and Synthetic Spirobutenolides and Spirobutyrolactones

Yadav

Pratap

Ram³

2020

Asian J Org Chem

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Spirobutenolides and spirobutyrolactones structural motifs are widespread in various natural products that exhibit a broad array of biological activities. Additionally, their synthetic analogues also serve as biologically active compounds and building blocks of complex molecules. Owing to the wide range of pharmacological activities and structural diversity of the spirobutenolides and spirobutyrolactones, various efficient synthetic methodologies have been established to construct such interesting scaffolds. In the past decades, numerous total syntheses of spirobutenolides and spirobutyrolactones containing natural products have been reported. Structurally diverse spirobutenolides and spirobutyrolactones have been synthesized by using singlet oxygen, Mannich reaction, aldol condensation, rearrangement reaction , Reformatsky reaction, Michael-addition cyclization, Diels-Alder reaction, photocyclization reaction, and pericyclic reactions. Recently, metal-catalyzed cyclization, photocatalyzed radical cyclization, Baylis-Hillman reaction, asymmetric organocatalysis, NHC catalysis, ring contraction reactions, and hypervalent iodine catalysis have emerged as powerful tools to architect these nuclei. This review gives an overview of advancements in chemically and biologically relevant spirobutenolides and spirobutyrolactones of natural and synthetic origin. It also covers the newer methodologies for the construction of natural as well as synthetic spirobutenolides and spirobutyrolactones along with their potential applications.

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Section: Important Natural Products Containing Spiro δ à Butenolides mentioning

confidence: 99%

Section: Important Natural Products Containing Spiro δ−Butenolides Anmentioning

confidence: 99%

Natural and Synthetic Spirobutenolides and Spirobutyrolactones

Yadav

Pratap

Ram³

2020

Asian J Org Chem

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“…Many different methods for their synthesis by de novo ring construction have been reported. Examples include cyclization of α,β-unsaturated γ-amino acids, [9] Mo-catalyzed reductive coupling of 1,2-diketones with α-ketoamides, [10] ring-closing metathesis of Nallylacrylamides, [11] radical ipso-cyclizations, [12] aminolysis of 2,5-dimethoxydihydrofuran, [13] dehydroiodination of 4-iodopyrrolidin-2-ones [14] and catalytic methods employing Pt, [15] Pd [16] and Fe. [17] Methods for transformation of pyrroles into Δ 3 -pyrrol-2-ones are less numerous, but approaches have been reported that rely on the reaction of a preexisting substituent at the pyrrole 2-position.…”

Section: Introductionmentioning

confidence: 99%

Unusual Regio‐ and Chemoselectivity in Oxidation of Pyrroles and Indoles Enabled by a Thianthrenium Salt Intermediate

Hann,

Lyall,

Kociok‐Köhn

et al. 2024

Angewandte Chemie

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A dearomative oxidation of pyrroles to Δ3‐pyrrol‐2‐ones is described, which employs a sulfoxide as oxidant, in conjunction with a carboxylic acid anhydride and a Brønsted acid additive. 3‐Substituted pyrroles undergo regioselective oxidation to give the product isomer in which oxygen has been introduced at the more sterically hindered position. This counterintuitive regioselectivity is rationalized by a proposed mechanism that proceeds by initial thianthrenium introduction at the less‐hindered pyrrole α‐position, followed by distal attack of an oxygen nucleophile and subsequent elimination of thianthrene. Furthermore, the same reaction conditions are also able to effect a chemoselective oxidation of indoles to indolin‐3‐ones and additionally of indolin‐3‐ones to 2‐hydroxyindolin‐3‐ones. Here again, the observed regio‐ and chemoselectivities are rationalized through the intermediacy of a thianthrenium salt.

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“… − Phenylglyoxylic acid was also recently reported as an effective PS for the preparation of 3a – c benzyl esters in batch . Paraconic acids are synthetic or naturally occurring, and many of them are endowed with promising biological activities. , Compounds 3a – c are currently commercially available and are reported as building blocks for the preparation of biologically relevant molecules. , …”

Section: Introductionmentioning

confidence: 99%

Continuous-Flow Preparation of γ-Butyrolactone Scaffolds from Renewable Fumaric and Itaconic Acids under Photosensitized Conditions

Gérardy

Winter

Horn

et al. 2017

Org. Process Res. Dev.

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The method and results described herein concern the photosensitized addition of various alcohols to renewable platform fumaric and itaconic acids under scalable continuous-flow conditions in glass micro-and mesofluidic reactors. Alcohols were used both as reagents and as solvents, thus contributing to a reduced environmental footprint. Process parameters such as the temperature, light intensity, and the nature as well as amount of the photosensitizer were assessed under microfluidic conditions and, next, transposed to a lab-scale mesofluidic reactor connected with an in-line NMR spectrometer for real-time reaction monitoring. Substituted γ-butyrolactones, including spiro derivatives with unique structural features, were obtained with quantitative conversion of the starting materials and in 47−76% isolated yields. The model photoaddition of isopropanol to fumaric acid was next successfully transposed in a pilot-scale continuous-flow photoreactor to further demonstrate scalability.

show abstract

Convenient synthesis of α,β-unsaturated γ-butyrolactones and γ-butyrolactams via decarboxylative iodination of paraconic acids and β-carboxyl-γ-butyrolactams using 1,3-diiodo-5,5-dimethylhydantoin

Cited by 10 publications

References 88 publications

Natural and Synthetic Spirobutenolides and Spirobutyrolactones

Natural and Synthetic Spirobutenolides and Spirobutyrolactones

Unusual Regio‐ and Chemoselectivity in Oxidation of Pyrroles and Indoles Enabled by a Thianthrenium Salt Intermediate

Continuous-Flow Preparation of γ-Butyrolactone Scaffolds from Renewable Fumaric and Itaconic Acids under Photosensitized Conditions

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