Preparation and properties of a novel solution of hydrogen bromide (HBr) in 1,4-dioxane: An alternative reagent to HBr gas without protic solvents

Nishio, Yuya; Mifune, Ryota; Sato, Takaaki; Ishikawa, Seiichi; Matsubara, Hiroshi

doi:10.1016/j.tetlet.2017.02.020

Cited by 9 publications

(3 citation statements)

References 25 publications

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“…To examine the feasibility of this synthetic route, the synthesis of racemic toxicodenane A ( 1 ) and its analogues was carried out first. Methylation of 20 according to a known procedure, , followed by alkylation with 2-(2-bromoethyl)-1,3-dioxolane 21 that could be synthesized via a one-step procedure from acrolein, gave 2,2-disubstituted 1,3-cyclohexanedione 22 (Scheme ). The desymmetric reduction of 22 with DIBALH gave 3-hydroxy cyclohexanone 23 in an excellent diastereoselectivity (ca.…”

Section: Results and Discussionmentioning

confidence: 99%

“…To examine the feasibility of this synthetic route, the synthesis of racemic toxicodenane A (1) and its analogues was carried out first. Methylation of 20 according to a known procedure, 2,5 followed by alkylation with 2-(2-bromoethyl)-1,3-dioxolane 21 that could be synthesized via a one-step procedure from acrolein, 6 For the construction of the oxa-bridged bicyclic ring system from 25, a cascade sequence involving transacetalation and Prins cyclization was investigated. Prins cyclization has been extensively investigated and used for the construction of polycyclic compounds, including complex natural products.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Synthetic Studies on the Synthesis of Toxicodenane A and 8,11-epi-Toxicodenane A

Qin

Han

2022

J. Org. Chem.

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The diverse synthesis of oxatricyclotridecanes and oxatricyclododecanes, which are the core structures of toxicodenane A and its skeletal analogues, via a unified manner is presented. The stereochemistry at the bridgehead position of the oxa-bridged bicycle could be efficiently controlled through a diastereoselective anti- and syn-Grignard allylation reaction by appropriately tuning the reaction conditions such as the solvent, the counterion of the Grignard reagent, the substrate, or a combination of these. The ring size could be precisely elaborated via a Lewis acid-mediated intramolecular transacetalation and Prins cyclization cascade reaction by varying the steric hindrance of olefin moiety. Namely, substrates bearing a terminally unsubstituted olefinic functionality afforded oxatricyclotridecanes with an overwhelming preference, while those bearing a dimethyl-substituted olefinic group produced exclusively oxatricyclododecanes. The wide utility and generality of the above key transformations are highlighted by the applications in the unified synthesis of (±)-toxicodenance A, (+)-toxicodenane A, (+)-8,11-epi-toxicodenane A, and other oxatricyclic cores with different stereochemistries and ring sizes.

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Section: Results and Discussionmentioning

confidence: 99%

“…To examine the feasibility of this synthetic route, the synthesis of racemic toxicodenane A (1) and its analogues was carried out first. Methylation of 20 according to a known procedure, 2,5 followed by alkylation with 2-(2-bromoethyl)-1,3-dioxolane 21 that could be synthesized via a one-step procedure from acrolein, 6 For the construction of the oxa-bridged bicyclic ring system from 25, a cascade sequence involving transacetalation and Prins cyclization was investigated. Prins cyclization has been extensively investigated and used for the construction of polycyclic compounds, including complex natural products.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthetic Studies on the Synthesis of Toxicodenane A and 8,11-epi-Toxicodenane A

Qin

Han

2022

J. Org. Chem.

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“…The authors have cited additional references within the Supporting Information. [61][62][63][64][65]67,68,[68][69][70][71][72][73][74][75][76][77]…”

Section: Supporting Informationmentioning

confidence: 99%

Bioresponsive pseudoGlucosinolates (psGSLs) release Isothiocyanates (ITCs) in the Presence of Nitroreductases

Jimidar,

Ganskow,

Kagho

et al. 2024

Preprint

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Glucosinolates (GSLs) are secondary metabolites produced as part of an herbivore defence system in plants of the order Brassicales. GSLs release isothiocyanates (ITCs) upon activation by the myrosinase. Beyond their herbivore feeding deterrent properties, these ITCs have multiple interesting bioactivities. However, their release is limited by the presence of myrosinase. Here, we report the concept of pseudoglucosinolates (psGSLs) hijacking the natural release mechanism of GSLs for the release of ITCs and adapting it to nitroreductase as triggering enzymes. We provide the proof-of-concept for nitroreductase-responsive psGSLs and demonstrate their potential for peptide labelling and ITC-prodrug approaches.

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Iridium‐katalysierte Hydrochlorierung und Hydrobromierung von Alkinen durch Shuttlekatalyse

Bismuto

Morandi

2020

Angewandte Chemie

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Hier beschreiben wir zwei verschiedene Methoden zur Synthese von Vinylhalogeniden über eine Shuttlekatalysebasierte Iridium-katalysierte Transfer-Hydrohalogenierung nichtaktivierter Alkine.Die Verwendung von 4-Chlorbutan-2on oder tert-Butylhalogenid als Donoren von Halogenwasserstoffen hat es ermçglicht, diese Umwandlung in Abwesenheit korrosiver Reagenzien wie Halogenwasserstoff oder Säurechloriden durchzuführen. Daher verbessern diese Reaktionen die Toleranz gegenüber funktionellen Gruppen sowie Sicherheitsaspekte verglichen zum aktuellen Stand der Forschung. Dies hat den Zugang zu Alkenylhalogenidverbindungen mit säureempfindlichen Gruppen wie tertiären Alkoholen, Silylethern und Acetalen ermçglicht. Der synthe-tischeW ert dieser Methoden wurded urch eine Synthese im Gramm-Maßstab,d ie mit einer geringen Katalysatorbeladung durchgeführt werden konnte,gezeigt. Schema 1. Kontext dieser Arbeit.

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Preparation and properties of a novel solution of hydrogen bromide (HBr) in 1,4-dioxane: An alternative reagent to HBr gas without protic solvents

Cited by 9 publications

References 25 publications

Synthetic Studies on the Synthesis of Toxicodenane A and 8,11-epi-Toxicodenane A

Synthetic Studies on the Synthesis of Toxicodenane A and 8,11-epi-Toxicodenane A

Bioresponsive pseudoGlucosinolates (psGSLs) release Isothiocyanates (ITCs) in the Presence of Nitroreductases

Iridium‐katalysierte Hydrochlorierung und Hydrobromierung von Alkinen durch Shuttlekatalyse

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