Gallium-mediated allyl transfer from bulky homoallyl alcohol to aldehydes or alkynes: Control of dynamic σ-allylgalliums based on retro-allylation reaction

Hayashi, Sayuri; Hirano, Koji; Yorimitsu, Hideki; Oshima, Koichiro

doi:10.1016/j.jorganchem.2006.08.047

Cited by 13 publications

(1 citation statement)

References 33 publications

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“…Moreover, retroallylation initiated from zinc alkoxides is applicable to cyclic homoallylic alcohols. 28 Later, Oshima found that retro-allylation can also be mediated by zirconium 29 and gallium, 30,31 whereby interesting stereospecificity is observed in the latter case. The gallium-chloridemediated reaction of erythro-10 with benzaldehyde produces erythro-11 in a high diastereomeric ratio (Scheme 6a).…”

Section: With Main Group Metalsmentioning

confidence: 99%

Carbon–Carbon Bond Cleavage at Allylic Positions: Retro-allylation and Deallylation

Nogi

Yorimitsu

2020

Chem. Rev.

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The development of C−C bond-cleaving transformations is an issue in modern organic chemistry that is as challenging as it is important. Among these transformations, the retroallylation and deallylation of allylic compounds are uniquely intriguing methods for the cleavage of C−C σ bonds at the allylic position. Retro-allylation is regarded as a prospective method for the generation of highly valuable regio-and stereodefined allylic metal compounds. Because the C−C cleavage proceeds via a favorable six-membered chairlike transition state, the regio-and stereochemical information on the starting homoallylic alcohols can be transferred onto the products. Moreover, retro-allylation can also be achieved using enantioselective C−C cleavage powered by chiral catalysts for the synthesis of enantiomerically enriched compounds. As a result of these attractive features, retro-allylation has wide utility in regio-, stereo-, and enantioselective synthesis. Deallylation is C−C σ-bond cleavage involving the departure of an allylic fragment and the formation of a relatively stable carbanion or radical, and it proceeds via either oxidative addition to a low-valent metal or an addition/β-elimination cascade. The removal of the versatile allylic group might seem to be unproductive; however, this unique transformation offers the opportunity of using the allylic group as a protective group for acidic C−H bonds. This Review aims to exhibit the synthetic utility as well as the uniqueness of these two C−C σ-bond cleavage methods by presenting a wide range of transformations of allylic compounds with the aid of main group metals, transition-metal catalysts, and radical species.

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Section: With Main Group Metalsmentioning

confidence: 99%

Carbon–Carbon Bond Cleavage at Allylic Positions: Retro-allylation and Deallylation

Nogi

Yorimitsu

2020

Chem. Rev.

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Retro‐allylation and Deallylation

Yorimitsu

2015

Cleavage of Carbon‐Carbon Single Bonds by Transition Metals

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Rhodium‐Catalyzed Allylation of Aldehydes with Homoallylic Alcohols by Retroallylation and Isomerization to Saturated Ketones with Conventional or Microwave Heating

Sumida

Takada

Hayashi

et al. 2007

Chemistry An Asian Journal

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The treatment of an aldehyde with a tertiary homoallylic alcohol at 100-250 degrees C in the presence of cesium carbonate and a rhodium catalyst leads to allyl transfer from the homoallylic alcohol to the aldehyde. The process includes Rh-mediated retroallylation to form an allyl rhodium species as the key intermediate. The homoallylic alcohol formed initially through allyl transfer is converted under the reaction conditions into the corresponding saturated ketone when bulky ligands are used. Microwave heating at 250 degrees C accelerates the reaction significantly.

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Gallium-mediated allyl transfer from bulky homoallyl alcohol to aldehydes or alkynes: Control of dynamic σ-allylgalliums based on retro-allylation reaction

Cited by 13 publications

References 33 publications

Carbon–Carbon Bond Cleavage at Allylic Positions: Retro-allylation and Deallylation

Carbon–Carbon Bond Cleavage at Allylic Positions: Retro-allylation and Deallylation

Retro‐allylation and Deallylation

Rhodium‐Catalyzed Allylation of Aldehydes with Homoallylic Alcohols by Retroallylation and Isomerization to Saturated Ketones with Conventional or Microwave Heating

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