New procedures for the selective synthesis of 2(2H)-pyranone derivatives and 3-aryl-4-iodoisocoumarins

Biagetti, Matteo; Bellina, Fabio; Carpita, Adriano; Stabile, Paolo; Rossi, Renzo

doi:10.1016/s0040-4020(02)00469-6

Cited by 108 publications

(27 citation statements)

References 49 publications

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“…Among these, the Sonogashira type coupling followed by the electrophilic or transition metal mediated cyclization of the resulting alkynes 22 (Fig. 7) possessing a carboxylate or an equivalent group in proximity to the triple bond has emerged as one of the most attractive process for the construction of the isocoumarin ring 23 [14][15][16] amides in the presence of a number of reagents including mineral acids, transition metal catalysts or halogens. Each of these methodologies will be discussed in the following sections.…”

Section: The Journey Of Isocoumarin Synthesismentioning

confidence: 99%

Isocoumarin and Its Derivatives: An Overview on their Synthesis and Applications

Pal¹,

Chatare²,

Pal³

2011

COC

185

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The prevalence of isocoumarins in numerous natural products that exhibit a wide range of biological activities has generated a continued and enormous interest among synthetic and medicinal chemists. The isocoumarin framework represents one of the privileged structures for the development of natural product-inspired compounds of potential biological interest. Considerable efforts have been devoted towards the synthesis of isocoumarins via either traditional or transition-metal catalyzed reactions. Among the metal catalyzed reactions, the use of Cu, Pd, Ag, Ru, Rh or Ir salts/complexes for the construction of isocoumarin ring are noteworthy. Among the other methodologies, halo-lactonization emerged as a practical process. Apart from preparing a variety of isocoumarins and thienopyranones, synthesis of naturally occurring and bioactive isocoumarins have been carried out by using cutting edge technologies. This review article will briefly cover all these aspects along with the synthetic utility of isocoumarins, highlighting recent developments.

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Section: The Journey Of Isocoumarin Synthesismentioning

confidence: 99%

Isocoumarin and Its Derivatives: An Overview on their Synthesis and Applications

Pal¹,

Chatare²,

Pal³

2011

COC

185

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“…In all cases described in the literature, the synthesis of butenolides, pyran-2-ones, phthalides and isocoumarins starting from b-iodopropenoic acid derivatives and alkynes using copper as catalyst has been performed in two separate steps: (i) coupling of (Z)-3-iodoprop-A C H T U N G T R E N N U N G enoic acid derivatives with terminal alkynes, typically by a Sonogashira-type reaction, and (ii) cyclization mediated by metal complexes, [16] bases, [17] and halogen. [18] In addition, our interest in the field [19] has focused on an intramolecular addition of carboxylic acids to allenylstannanes for the construction of 3-substituted isocoumarins and a-pyrones. [20] We also described the synthesis of dienoic acids and enynes bearing a carboxylic acid function from b-iodovinylic acids and vinyltin or alkynylzinc reagents.…”

Section: Full Papersmentioning

confidence: 99%

Copper‐Catalyzed Preparation of γ‐Alkylidenebutenolides and Isocoumarins under Mild Palladium‐Free Conditions

et al. 2009

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A general and efficient copper(I)-catalyzed cross-coupling and heterocyclization reaction of terminal alkynes and b-iodo-a,b-unsaturated acid derivatives has been developed under very mild conditions. This method provides easy access from good to excellent yields of a variety of 5-ylidenebutenolides and 3-substituted isocoumarins with excellent regioand stereoselectivity. This procedure does not require the use of any expensive supplementary additives, and is palladium-free.

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“…The excellent reproducibility and scalability of this Negishi coupling [40,41] were prerequisites for the success of the total synthesis campaign.…”

Section: Preparation Of the Building Blocks-the Western Fragmentmentioning

confidence: 99%

Total Synthesis of Myxovirescin A₁

Fürstner¹,

Bonnekessel²,

Blank³

et al. 2007

Chemistry A European J

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A convergent total synthesis of the antibiotic macrolide myxovirescin A1 (1) is described that is largely based on reagent- and catalyst-controlled transformations. This includes a highly regioselective Negishi reaction of dibromo-alkene 48 with an alkynylzinc reagent, and a palladium catalyzed alkyl-Suzuki coupling of the resulting enyne derivative 12 with the 9-BBN-adduct derived from alkene 61. The latter was obtained via an asymmetric hydrogenation of the chlorinated beta-ketoester 49 and an anti-selective oxyallylation of the functionalized aldehyde 53 as the key steps. The preparation of the bis-borylated allyl-donor 57 used in the oxyallylation step, however, required careful optimization and led to important insights into the nature of the classical hydroborating agent "di(isopinocampheyl)borane (Ipc2BH)". It was unambiguously shown by X-ray crystallography that in the solid state this compound is dimeric, but it is prone to undergo an essentially quantitative mono-deborylation when dissolved in CH2Cl2 or benzene; its composition in ethereal solvents is even more complex as evident from 11B NMR data. Product 71 derived from 12 and 61 was elaborated into the enyne-yne derivative 75, which served as the substrate for an exquisitely selective ring closing alkyne metathesis reaction (RCAM) catalyzed by the molybdenum tris-amido complex 20 activated in situ with CH2Cl2. The resulting cyclic enyne 76 was subjected to a ruthenium catalyzed trans-hydrosilylation/proto-desilylation tandem. Although [Cp*Ru(MeCN)3]PF6 had previously been recommended as catalyst of choice for trans-hydrosilylation reactions of internal alkynes, this complex failed to afford the desired product, whereas its sterically less hindered congener [CpRu(MeCN)3]PF6 permitted the reaction to be performed in appreciable yield, but at the expense of a lower stereoselectivity. AgF-mediated proto-desilylation of the isomeric silanes 79 and 80 followed by cleavage of the remaining acetal protecting groups afforded myxovirescin A1 and its hitherto unknown 14Z-isomer 81, respectively.

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New procedures for the selective synthesis of 2(2H)-pyranone derivatives and 3-aryl-4-iodoisocoumarins

Cited by 108 publications

References 49 publications

Isocoumarin and Its Derivatives: An Overview on their Synthesis and Applications

Isocoumarin and Its Derivatives: An Overview on their Synthesis and Applications

Copper‐Catalyzed Preparation of γ‐Alkylidenebutenolides and Isocoumarins under Mild Palladium‐Free Conditions

Total Synthesis of Myxovirescin A₁

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New procedures for the selective synthesis of 2(2H)-pyranone derivatives and 3-aryl-4-iodoisocoumarins

Cited by 108 publications

References 49 publications

Isocoumarin and Its Derivatives: An Overview on their Synthesis and Applications

Isocoumarin and Its Derivatives: An Overview on their Synthesis and Applications

Copper‐Catalyzed Preparation of γ‐Alkylidenebutenolides and Isocoumarins under Mild Palladium‐Free Conditions

Total Synthesis of Myxovirescin A1

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Total Synthesis of Myxovirescin A₁