A new synthesis of β-keto-phenylsulfoxides

Monteiro, Hugo J.; Souza, João Pedro de

doi:10.1016/s0040-4039(00)72020-x

Cited by 38 publications

(5 citation statements)

References 7 publications

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“…In addition, this method represents a new approach for the synthesis of β-keto sulfoxides. Three general methods have been reported in the literature for the synthesis of β-keto sulfoxides, namely, i) the reaction of α-sulfinyl anions derived from sulfoxides with esters or nitriles, ii) the oxidation of β-thioethers, and iii) the addition of ketone enolates to sulfinate esters .…”

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confidence: 99%

First Synthesis of β-Keto Sulfoxides by a Palladium-Catalyzed Carbonylative Suzuki Reaction

et al. 2005

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[reaction: see text] An unprecedented palladium-catalyzed three-component cross-coupling reaction between alpha-bromo sulfoxide, carbon monoxide, and aromatic boronic acids provides a new and efficient approach to the synthesis of beta-ketosulfoxides. The reaction takes place under mild conditions with a wide range of variously substituted aryl and heteroaryl boronic acids. The carbonylative cross-coupling reaction is strongly favored over competing direct cross-coupling and homocoupling processes, except with boronic acids carrying strong electron-withdrawing substituents.

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confidence: 99%

First Synthesis of β-Keto Sulfoxides by a Palladium-Catalyzed Carbonylative Suzuki Reaction

et al. 2005

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“…The unreacted C9‐ketone of 11 was then used to construct the C8‐olefin of 12 . Namely, sulfoxide was attached at the C8 position by the reagent combination of KH and PhS(O)OMe, [17] and subsequently eliminated by treatment with Na 2 CO 3 in heated toluene, furnishing enone 12 . Dibromination of the olefin by Br 2 in CCl 4 , followed by pyridine‐promoted E1cB elimination converted 12 into α‐bromo enone 13 .…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of (−)‐Batrachotoxin Enabled by a Pd/Ag‐Promoted Suzuki–Miyaura Coupling Reaction

Watanabe,

Morozumi,

Mutoh

et al. 2023

Angew Chem Int Ed

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Batrachotoxin is an extremely potent cardio‐ and neurotoxic steroidal alkaloid found in certain species of frogs, birds, and beetles. The steroidal 6/6/6/5‐membered carbocycle (ABCD‐ring) is U‐shaped and functionalized with two double bonds, a six‐membered C3‐hemiacetal across the AB‐ring, a seven‐membered oxazepane on the CD‐ring, and a dimethylpyrrolecarboxy group at the D‐ring carbon chain. These structural features present an unusual and formidable synthetic challenge. Herein we report a total synthesis of batrachotoxin based on a newly devised convergent strategy. Enantiopure AB‐ring and D‐ring fragments were prepared and subjected to a crucial C(sp2)–C(sp2) coupling reaction. Although both C(sp2)‐centers were sterically encumbered by proximal tetrasubstituted carbons, Ag2O strongly promoted the Pd(PPh3)4‐catalyzed Suzuki‐Miyaura coupling reaction at room temperature, thereby connecting the two fragments without damaging their preexisting functionalities. Subsequent treatment with t‐BuOK induced Dieckmann condensation to cyclize the C‐ring. The judiciously optimized functionalizations realized oxazepane formation, carbon chain extension, and pyrrole carboxylic acid condensation to deliver batrachotoxin. Thus, the total synthesis was accomplished through a 22‐step sequence. Because of the efficiency in assembling the densely functionalized steroidal skeleton, the overall strategy and tactics developed here are expected to be widely applicable for constructing structurally complex steroids other than batrachotoxin.

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“…The required cyclohexenone esters 3 were prepared from cyclohexanones 1 as outlined in Scheme , either via bromination–elimination of δ-keto esters 2 (series a , b ; 55–60% overall yield) or by alkylation of a keto sulfoxide intermediate with methyl acrylate, followed by thermal elimination (series c – e ; ∼75% overall yield).…”

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A Practical Synthetic Route to Enantiopure 6-Substituted cis-Decahydroquinolines

et al. 2011

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A new synthesis of β-keto-phenylsulfoxides

Cited by 38 publications

References 7 publications

First Synthesis of β-Keto Sulfoxides by a Palladium-Catalyzed Carbonylative Suzuki Reaction

First Synthesis of β-Keto Sulfoxides by a Palladium-Catalyzed Carbonylative Suzuki Reaction

Total Synthesis of (−)‐Batrachotoxin Enabled by a Pd/Ag‐Promoted Suzuki–Miyaura Coupling Reaction

A Practical Synthetic Route to Enantiopure 6-Substituted cis-Decahydroquinolines

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