The Copper(I) Iodide-promoted Allylation of Vinylstannanes with Allylic Halides

Takeda, Takeshi; Matsunaga, Kazuma; Kabasawa, Yuki; Fujiwara, Tooru

doi:10.1246/cl.1995.771

Cited by 49 publications

(17 citation statements)

References 9 publications

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“…Piers and Wong demonstrated that the intramolecular coupling of alkenyl iodides with alkenyl stannanes can be carried out in the presence of a stoichiometric amount of CuCl. [285,286] Better results were later obtained with other Cu I salts under catalytic conditions. [287][288][289][290][291] As an illustration, the cross-coupling of 98 and methyl (E)-b-iodoacrylate (99) promoted by copper(i) thiophene-2-carboxylate (CuTC) furnished 100 (Scheme 51), an intermediate in the synthesis of formamicinone.…”

Section: Reactions Initiated By the Oxidative Addition Of Stannanes Tmentioning

confidence: 99%

The Mechanisms of the Stille Reaction

2004

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Eighteen years ago in Angewandte Chemie John K. Stille reviewed a novel methodology, which eventually became known by his name, for the coupling of organostannanes with organic electrophiles. Since then that seed has blossomed into a multifaceted methodology full of hidden possibilities to explore, discover, and enjoy. Very recent modifications are making synthetic wishes come true that were only dreamed of a few years ago. Moreover, as important advances are being made in the understanding of the mechanistic details of the process, it is becoming increasingly possible to apply this essential reaction and its new variants in a less empirical way. The purpose of this Review is to give a critical account of this progress.

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Section: Reactions Initiated By the Oxidative Addition Of Stannanes Tmentioning

confidence: 99%

The Mechanisms of the Stille Reaction

2004

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“…The chemical shift of the trimethylsilyl protons of the 2a-metha was observed at 0.18 ppm, but that of its Z-isomer was reported to appear at −0.17 ppm. [14] CuI-mediated cross-coupling of (Z)-(n-Bu) 3 SnCAr CHSiMe 3 1 with allyl halides in DMSO-THF The transmetallation of Sn → Cu → Pd suggested by Liebeskind et al [59] in the reaction of simple vinylstannane with organic halides and the copper(I) iodide-mediated reaction of simple vinylstannane with allyl halides reported by Takeda et al [60] stimulated us to examine the copper(I) iodide-mediated crosscoupling of (Z)-silyl(stannyl)ethenes 1 with allyl halides in a polar aprotic solvent, particularly a DMSO-THF solvent. No precedent has been reported for the reaction of 1 with allyl halides in the sole presence of copper(I) halide.…”

Section: Optimization Of Reaction Conditions Outlined In Schemementioning

confidence: 95%

“…Spectral data ( 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, LRMS and HRMS) agreed well with those from the expected structure. Copper(I) iodide-mediated reaction in DMF or in DMSO-THF solvent [60] readily occurred at room temperature to give 3a in 43-80% yields. Among them, CuI-mediated reaction in DMSO-THF recorded the highest yield (80% isolated-yield) of 3a.…”

Section: Cui-mediated Reaction Of (Z)-(n-bu) 3 Sncar Chsime 3 1 With mentioning

confidence: 99%

Stereospecific synthesis of a family of novel (E)‐2‐aryl‐1‐silylalka‐1,4‐dienes or (E)‐4‐aryl‐5‐silylpenta‐1,2,4‐trienes via a cross‐coupling of (Z)‐silyl(stannyl)ethenes with allyl halides or propargyl bromide

Sasaki

Endo

Noguchi

et al. 2008

Applied Organom Chemis

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Stereospecific synthesis of a family of novel (E)-2-aryl-1-silylalka-1,4-dienes or (E)-4-aryl-5-silylpenta-1,2,4-trienes via a crosscoupling of (Z)-silyl(stannyl)ethenes with allyl halides or propargyl bromide is described. In the reaction with allyl bromide, either a Pd(dba) 2 -CuI combination (dba, dibenzylideneacetone) in DMF or copper(I) iodide in DMSO-THF readily catalyzes or mediates the coupling reaction of (Z)-silyl(stannyl)ethenes at room temperature, producing novel vinylsilanes bearing an allyl group β to silicon with cis-disposition in good yields. Allyl chlorides as halides can be used in the CuI-mediated reaction. CuI alone much more effectively mediates the cross-coupling reaction with propargyl bromide in DMSO-THF at room temperature compared with a Pd(dba) 2 -CuI combination catalysis in DMF, providing novel stereodefined vinylsilanes bearing an allenyl group β to silicon with cis-disposition in good yields.

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“…No precedent was found for the copper(I) iodide-mediated cross-coupling of (Z)-(R 3 Sn)CR CH(GeR 3 ) with allylic halides, while copper (I) iodide 52 has been reported to mediate the coupling reaction of a simple vinylstannane, 1-(tri-n-butylstannyl)-1-phenylethene, with an allyl halide. (Z)-Germyl(stannyl)ethenes 1 are much more congested compared with 1-(tri-n-butylstannyl)-1-phenylethene.…”

Section: Cui-mediated Cross-coupling Of (Z)-germyl(stannyl)ethenes Wimentioning

confidence: 99%

Synthesis of novel stereodefined vinylgermanes bearing an allyl group or an allenyl group: (E)‐2‐aryl‐1‐germylalka‐1,4‐dienes and (E)‐4‐aryl‐5‐germylpenta‐1,2,4‐trienes

Kato

Senda

Makihara

et al. 2007

Applied Organom Chemis

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Stereodefined synthesis of an unprecedented family of vinylgermanes bearing an allyl group, (E)-2-aryl-1-germylalka-1,4-dienes, or an allenyl group, (E)-4-aryl-5-germylpenta-1,2,4-trienes, via a cross-coupling reaction of (Z)-germyl(stannyl)ethenes with the respective allyl halide (Br, Cl) and propargyl bromide is described. In the reaction with allyl halides, either a Pd(dba) 2 -CuI combination (dba: dibenzylideneacetone) or CuI alone readily catalyzes or mediates the coupling reaction of (Z)-germyl(stannyl)ethenes, producing the novel vinylgermanes bearing an allyl group. The thienyl group or hydroxy group of the (Z)-germyl(stannyl)ethene survives the reaction. Copper(I) iodide alone readily mediates the reaction with allyl chloride or methallyl chloride upon addition of sodium bromide to produce the respective cross-coupled product in good yield. In contrast, crotyl halides (Br, Cl) or prenyl chloride couple with/without allylic transposition in the bromide or the chloride. In the reaction with propargyl bromide, a Pd(dba) 2 and CuI combination efficiently drives the coupling reaction of (Z)-germyl(stannyl)ethenes in NMP (N-methylpyrrolidone), providing the stereochemically defined allenyl vinylgermanes, (E)-4-aryl-5-germylpenta-1,2,4-trienes, in good yields.

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The Copper(I) Iodide-promoted Allylation of Vinylstannanes with Allylic Halides

Cited by 49 publications

References 9 publications

The Mechanisms of the Stille Reaction

The Mechanisms of the Stille Reaction

Stereospecific synthesis of a family of novel (E)‐2‐aryl‐1‐silylalka‐1,4‐dienes or (E)‐4‐aryl‐5‐silylpenta‐1,2,4‐trienes via a cross‐coupling of (Z)‐silyl(stannyl)ethenes with allyl halides or propargyl bromide

Synthesis of novel stereodefined vinylgermanes bearing an allyl group or an allenyl group: (E)‐2‐aryl‐1‐germylalka‐1,4‐dienes and (E)‐4‐aryl‐5‐germylpenta‐1,2,4‐trienes

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