Palladium-catalyzed Mizoroki–Heck Reactions of 2-Methylene-1,3-dithiane 1-Oxide with Aryl Iodides

Morita, Eiji; Iwasaki, Masayuki; Yoshida, Suguru; Yorimitsu, Hideki; Oshima, Koichiro

doi:10.1246/cl.2009.624

Cited by 9 publications

(1 citation statement)

References 17 publications

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“…The reaction was applicable with an acyclic ketene dithioacetal monoxide to provide 3 j , albeit in lower yield. With a higher catalyst loading, aryl‐substituted 2 13 reacted efficiently, regardless of the electronics of the aryl groups ( 3 k – 3 p ). It is noteworthy that the reaction can be performed on a large scale to provide 3 n in high yield.…”

Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed Extended Pummerer Reactions of Ketene Dithioacetal Monoxides with Alkynyl Sulfides and Ynamides with an Accompanying Oxygen Rearrangement

Murakami¹,

Imoto²,

Matsubara³

et al. 2013

Chemistry A European J

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The first examples of metal-catalyzed extended Pummerer reactions through the activation of sulfoxides are described. The copper-catalyzed reactions of ketene dithioacetal monoxides with alkynyl sulfides and ynamides provided a wide variety of γ,γ-disulfanyl-β,γ-unsaturated carbonyl compounds with an accompanying oxygen rearrangement. The products can be easily converted into 1,4-dicarbonyl compounds and substituted heteroaromatics. DFT calculations and mechanistic experiments revealed a new interesting stepwise addition/oxygen rearrangement mechanism.

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Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed Extended Pummerer Reactions of Ketene Dithioacetal Monoxides with Alkynyl Sulfides and Ynamides with an Accompanying Oxygen Rearrangement

Murakami¹,

Imoto²,

Matsubara³

et al. 2013

Chemistry A European J

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Ketene Dimethyl Thioacetal Monoxide

Dieter

Lafantaisie

et al. 2013

Encyclopedia of Reagents for Organic Synthesis

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Reversed‐Polarity Synthesis of Diaryl Ketones through Palladium‐Catalyzed Direct Arylation of 2‐Aryl‐1,3‐dithianes

Yucel

Walsh

2014

Adv Synth Catal

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An umpolung approach to the synthesis of diaryl ketones has been developed based on in situ generation of acyl anion equivalents and their catalytic arylation. This method entails the base promoted palladium catalyzed direct C–H arylation of 2 The resulting 2,2-diaryl-1,3-dithianes with aryl bromides. Use of MN(SiMe3)2 (M=Li, Na) base results in reversible deprotonation of the weakly acidic dithiane. In the presence of a Pd(NiXantphos)-based catalyst and aryl bromide, cross-coupling of the metallated 2-aryl-1,3-dithiane takes place under mild conditions (2 h at rt) with yields as high as 96%. The resulting 2,2-diaryl-1,3-dithianes were converted into diaryl ketones by either molecular iodine, N-bromo succinimide (NBS) or Selectfluor in the presence of water. The dithiane arylation/hydrolysis can be performed in a one-pot procedure to yield a good to excellent yields. This method is suitable for rapid and large-scale synthesis of diaryl ketones. A one-pot preparation of anti-cholesterol drug fenofibrate (TriCor®) has been achieved on 10.0 mmol scale in 86% yield.

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Palladium-catalyzed Mizoroki–Heck Reactions of 2-Methylene-1,3-dithiane 1-Oxide with Aryl Iodides

Abstract: Treatment of 2-methylene-1,3-dithiane 1-oxide with aryl iodides under palladium catalysis in the presence of potassium carbonate and tetrabutylammonium bromide leads to the Mizoroki–Heck arylation to yield 2-(arylmethylene)-1,3-dithiane 1-oxides in high yields.

Cited by 9 publications

References 17 publications

Copper‐Catalyzed Extended Pummerer Reactions of Ketene Dithioacetal Monoxides with Alkynyl Sulfides and Ynamides with an Accompanying Oxygen Rearrangement

Copper‐Catalyzed Extended Pummerer Reactions of Ketene Dithioacetal Monoxides with Alkynyl Sulfides and Ynamides with an Accompanying Oxygen Rearrangement

Ketene Dimethyl Thioacetal Monoxide

Reversed‐Polarity Synthesis of Diaryl Ketones through Palladium‐Catalyzed Direct Arylation of 2‐Aryl‐1,3‐dithianes

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