Model studies for the synthesis of the antibiotic lactonamycin and the discovery of new reactions and mechanisms for the construction of substituted heterocycles

Parsons, Philip J.; Board, Jonathan; Faggiani, Davide; Hitchcock, Peter B.; Preece, Lewis; Waters, Alexander J.

doi:10.1016/j.tet.2010.05.051

Cited by 13 publications

(6 citation statements)

References 23 publications

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“…a). 2 In contrast, substituted propropargylic electrophiles are only known to react in an S N 2′ fashion 3 to form the corresponding allene, regardless of the nature of the leaving group (R 2 or R 3 ≠ H, Eq. b).…”

mentioning

confidence: 99%

Re-orienting coupling of organocuprates with propargyl electrophiles from S_N2′ to S_N2 with stereocontrol

Trost

Debien

2016

Chem. Sci.

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Diorganocuprate(I) reagents derived from lithiated heterocycles and CuCN react with enantioenriched secondary propagryl bromides to give the corresponding propargylated heterocycles. While propargyl electrophiles typically undergo SN2′ displacement, this transformation represents the first example of the reaction of hard carbanions with propargyl eletrophiles in an SN2 fashion and occurs with excellent levels of stereoinversion. The new method was applied to the formal synthesis of (+)-frondosin B.

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mentioning

confidence: 99%

Re-orienting coupling of organocuprates with propargyl electrophiles from S_N2′ to S_N2 with stereocontrol

Trost

Debien

2016

Chem. Sci.

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“…In a previous publication, it was shown that the replacement of protons with deuterium led to a threefold decrease in the rate of reaction. 9 Furthermore, the introduction of radical traps did not lead to the expected trapped products. These observations are consistent with the concerted mechanism suggested by other groups working in this area.…”

Section: Syn Thesismentioning

confidence: 95%

“…Further investigations to extend our original findings were carried out (Scheme 4). 9,14 Accordingly, both the amide 10 and ester 11 cyclisation precursors cyclised to their respective furan products 12 and 13. There is, however, a significant difference in the rate of reaction between the two substrates.…”

Section: Figure 1 Structure Of the Antibiotic Lactonamycinmentioning

confidence: 99%

“…Alcohol 14 was con- Multiple pathways have been proposed to account for this transformation (Scheme 11). 9 The first step of the mechanistic proposal can be divided into either a concerted or stepwise pathway. In the concerted pathway, the labelled precursor 35 proceeds directly in one step via a propargylic ene reaction to the alkenyl allene 36, which can then undergo a Diels-Alder cyclisation to provide the observed product 37.…”

Section: Scheme 7 Unsuccessful Cyclisations Of Derivatives Of 18mentioning

confidence: 99%

“…2 These time-resolved sequences 3 can be designed by carefully evaluating the functional group reactivity in the starting materials, and as such they can be initiated using a variety of techniques, including photochemistry, 4 radical chemistry, 5 metal catalysis, 6 organocatalysis, 7 and thermolysis. 8,9 Given the importance of aromatic polyfunctional arrays in the chemical industries, we sought to develop new domino processes for the preparation of the aforementioned ring systems. This paper is concerned with the evaluation of the scope and limitations of our domino process for the prepa-ration of polysubstituted aromatic rings.…”

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confidence: 99%

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Approaches to the Synthesis of Highly Substituted Aromatic and Fused Rings: Metal-Catalysed versus Thermal Cyclisation

et al. 2017

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A domino reaction has been used for the construction of lactonamycin derivatives. This research led to a comparison study between palladium-mediated cascade cyclisations and thermal alkyne [2+2+2] cyclisations. A palladium-mediated cyclisation of alkenyl bromides with alkynes and furans has been shown to furnish highly substituted aromatic rings. Penta- and hexasubstituted aromatic rings have also been prepared by the thermolysis of suitably substituted alkynes under microwave conditions. Tetrasubstituted pyridines can also be prepared using nitriles instead of alkynes. This work will provide a new and interesting array of drug templates; mechanistic details are discussed for both reaction series.

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Recent Advances in Total Synthesis of Bioactive Furo[3,2‐b]furanone Natural Products

et al. 2020

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The ubiquitous presence of highly oxygenated furo[3,2‐b]furanone fragments in diverse natural products with wide range of biological activities such as anti‐cancer, anti‐HIV, anti‐microbial activities, etc., has augmented their appeal both for synthetic and medicinal chemistry campaigns. Enticed by their potent biological activities and challenging polycyclic architecture, total synthesis of furo[3,2‐b]furanone natural products has witnessed intense activity in recent years with many notable achievements in the synthesis of structurally embellished family of bioactive metabolites such as plakortones, lactonamycines, schisanartanes, etc. While presenting a comprehensive account of post‐2000 syntheses of these natural products, through strategic and nuanced use of modern tools of organic synthesis, this review also aims to stimulate interest in exploring the diversity space around these natural products for newer applications.

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Model studies for the synthesis of the antibiotic lactonamycin and the discovery of new reactions and mechanisms for the construction of substituted heterocycles

Cited by 13 publications

References 23 publications

Re-orienting coupling of organocuprates with propargyl electrophiles from S_N2′ to S_N2 with stereocontrol

Re-orienting coupling of organocuprates with propargyl electrophiles from S_N2′ to S_N2 with stereocontrol

Approaches to the Synthesis of Highly Substituted Aromatic and Fused Rings: Metal-Catalysed versus Thermal Cyclisation

Recent Advances in Total Synthesis of Bioactive Furo[3,2‐b]furanone Natural Products

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Model studies for the synthesis of the antibiotic lactonamycin and the discovery of new reactions and mechanisms for the construction of substituted heterocycles

Cited by 13 publications

References 23 publications

Re-orienting coupling of organocuprates with propargyl electrophiles from SN2′ to SN2 with stereocontrol

Re-orienting coupling of organocuprates with propargyl electrophiles from SN2′ to SN2 with stereocontrol

Approaches to the Synthesis of Highly Substituted Aromatic and Fused Rings: Metal-Catalysed versus Thermal Cyclisation

Recent Advances in Total Synthesis of Bioactive Furo[3,2‐b]furanone Natural Products

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Product

Resources

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Re-orienting coupling of organocuprates with propargyl electrophiles from S_N2′ to S_N2 with stereocontrol

Re-orienting coupling of organocuprates with propargyl electrophiles from S_N2′ to S_N2 with stereocontrol