Synthesis of Isocoumarins and α-Pyrones via Tandem Stille Reaction/Heterocyclization

Cherry, Khalil; Parrain, Jean‐Luc; Thibonnet, J.; Duchêne, and Alain; Abarbri, Mohamed

doi:10.1021/jo050638z

Cited by 91 publications

(28 citation statements)

References 91 publications

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“…1,2-Dienyl-1-stannyl reagents were used in tandem intermolecular Stille-heterocyclization reactions affording isocoumarins (Eq. (3)) [8], indoles [9], and 2-pyridinones and (2H)-isoquinolin-1-ones [10].…”

Section: Carbon-carbon Bond-forming Reactions Via Transmetallationmentioning

confidence: 99%

Transition metals in organic synthesis: Highlights for the year 2005

Söderberg

2008

Coordination Chemistry Reviews

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Section: Carbon-carbon Bond-forming Reactions Via Transmetallationmentioning

confidence: 99%

Transition metals in organic synthesis: Highlights for the year 2005

Söderberg

2008

Coordination Chemistry Reviews

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“…A general route to 3-substituted isocoumarins from 2-iodobenzoic acids 278 has been described by Cherry and co-workers [33]. Treatment of 2-iodobenzoic acids 278 with various allenyltributyltin reagents 279 in the presence of palladium acetate, triphenylphosphine, and tetrabutylammonium bromide in dimethylformamide provided good yields of the corresponding 3-substituted isocoumarins 280 via a tandem Stille reaction and 6-endo-dig oxacyclisation (Scheme 4.11).…”

Section: Synthesis Of Isocoumarins Via Tandem Stille Reactionmentioning

confidence: 99%

Synthesis of Isocoumarins and Dihydroisocoumarins

Shahzad

2012

Springer Theses

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This chapter initially reviews methods for the preparation of isocoumarin derivatives and describes some previous synthetic methods. A new selenium-catalysed synthesis of isocoumarins is discussed and its application for preparation of a range of isocoumarins by reaction of stilbene carboxylic acids with diphenyl diselenide and a hypervalent iodine reagent is described. It was also discovered that dimethyl diselenide and diphenyl disulfide can be used in place of diphenyl diselenide. Using this modification the method was extended to prepare more challenging dihydroisocoumarins. Applications of Isocoumarins and DihydroisocoumarinsThe isocoumarin skeleton is part of many naturally occurring lactones which display a wide range of biological and pharmacological activities [1][2][3][4][5][6]. 3,4-Dihydroisocoumarins and their derivatives are compounds that widely exist in nature and serve as key intermediates in the synthesis of biologically active molecules. As these compounds are known to have a wide range of interesting activities such as antifungal, antiallergenic, antiulcer, and antimalarial activities, they are regarded as highly attractive molecules in organic chemistry [3][4][5][6]. 3-Aryl-isocoumarin derivatives constitute a pharmacologically important chemical entity which occurs in several natural products. These include thunberginol C, D, and E and hydrangenol [7,8]. Pharmacological activities of these natural products include the promotion of the adipogenesis of murine 3T3-L1 cells [7] and antiproliferative activity against mouse splenocytes [8]. Previous Synthesis of Isocoumarins and Dihydroisocoumarins Regiospecific Synthesis of Benzopyran-1-onesIn 1988, Hauser and co-workers [20] reported the synthesis of benzopyran-1-ones 248 from phthalaldehydic acids 244 and nitroalkanes (Scheme 4.1). The sequence permits a straightforward variation of both the 3-substituent and the pattern of functionalisation on the aromatic ring of the benzopyran ring system. The nitroalkyl isobenzofuranones 245 (obtained from condensation of 244 and nitroalkanes with triethylamine in DMSO) are treated with sodium borohydride in dimethyl sulfoxide providing the (nitroalkyl) benzoic acids 246 in 70-95 % yield. The benzopyran-1-ones 248 were obtained by the Nef reaction of 246 followed by intramolecular cyclisation of the resulting 247 and subsequent dehydration (Scheme 4.1). Stobbe condensations of homophthalates 249 with aldehydes have also been widely employed for the synthesis of benzopyran-1-ones 252 as shown in Scheme 4.2. Reactions of the homophthalate 249 with aromatic aldehydes gave good yields of the styryl half esters 250; however, the corresponding reaction with aliphatic aldehydes gave low yields. The additional steps necessary to convert 250 to 251 are harsh, and the overall yields of products using this approach are rather modest, especially for benzopyranones containing a 3-alkyl group 252.

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“…7,8 Although a number of preparative methods for dienamides 8 have appeared in the literatures, [8][9][10][11][12][13] and various heterocycles can be expected from their electrophilic cyclization reaction, few examples have been reported on this kind of investigation. 7,14,15 By treatment of our in situ generated 1-lithio-1,3-dienes 4 with isocyanates (both N-aryl isocyanates and N-alkyl isocyanates), 16,17 we developed an alternative synthesis of these conjugated unsaturated amides 8 ( Fig. 5) and studied their applications to the preparation of heterocycles via electrophilic cyclization.…”

Section: Reaction With Isocyanates Preparation Of Multi-substituted mentioning

confidence: 99%

1-Lithio-1,3-dienes: Useful Building Blocks for Cyclic Compounds

2007

Bulletin of the Chemical Society of Japan

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In this account, our recent results on the application of substituted 1-lithio-1,3-dienes as building blocks for the preparation of a wide variety of cyclic compounds and linear compounds are briefly summarized. Results have revealed that the essential factor which makes 1-lithio-1,3-diene derivatives useful and unique as building blocks is the intracooperation between the alkenyllithium moiety and the butadienyl skeleton, notwithstanding that the alkenyllithium moiety itself reacts with organic substrates in the usual way. In addition, the substitution patterns and the nature of the substituents on the butadienyl skeleton have been demonstrated to affect remarkably the reaction pathways of 1-lithio-1,3-diene derivatives.

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Synthesis of Isocoumarins and α-Pyrones via Tandem Stille Reaction/Heterocyclization

Cited by 91 publications

References 91 publications

Transition metals in organic synthesis: Highlights for the year 2005

Transition metals in organic synthesis: Highlights for the year 2005

Synthesis of Isocoumarins and Dihydroisocoumarins

1-Lithio-1,3-dienes: Useful Building Blocks for Cyclic Compounds

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