Claisen Rearrangement of Aliphatic Allyl Vinyl Ethers from 1912 to 2012: 100 Years of Electrophilic Catalysis

Rehbein, Julia; Hiersemann, Martin

doi:10.1055/s-0032-1316869

Cited by 59 publications

(1 citation statement)

References 142 publications

(191 reference statements)

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“…The similar consequence was noticed for Sc(OTf) 3 (Entry 5), and like the cases of other triflates like Mg(OTf) 2 , Yb(OTf) 3 , Gd(OTf) 3 (not shown in Table 4 ) [ 17 ], the total amounts of fluorinated compounds obtained after the reaction were only in a range of 40% to 60% including 5a in less than 5% yield. However, interesting to note is the fact that weakly acidic but non-nucleophilic 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) [ 18 ] promoted the desired transformation nicely to afford 5a in 66% yield after stirring for 3 days at room temperature (Entry 6).…”

Section: Resultssupporting

confidence: 75%

Base-Mediated Claisen Rearrangement of CF3-Containing Bisallyl Ethers

Hamada¹,

Matsunaga²,

Kawasaki‐Takasuka³

et al. 2021

Molecules

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We have previously clarified that the strongly electron-withdrawing CF3 group nicely affected the base-mediated proton shift of CF3-containing propargylic or allylic alcohols to afford the corresponding a,b-unsaturated or saturated ketones, respectively, which was applied this time to the Claisen rearrangement after O-allylation of the allylic alcohols with a CF3 group, followed by isomerization to the corresponding allyl vinyl ethers via the proton shift, enabling the desired rearrangement in a tandem fashion, or in a stepwise manner, the latter of which was proved to have attained an excellent diastereoselectivity with the aid of a palladium catalyst.

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Section: Resultssupporting

confidence: 75%

Base-Mediated Claisen Rearrangement of CF3-Containing Bisallyl Ethers

Hamada¹,

Matsunaga²,

Kawasaki‐Takasuka³

et al. 2021

Molecules

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(4+3) Cycloadditions of Allylic and Related Cations

Harmata,

Tu,

Clark

2024

Organic Reactions

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The reaction of allylic cations with 1,3‐dienes is formally equivalent to the Diels–Alder reaction but leads to seven‐membered rings. An allylic cation contains 2 pi electrons, and is thus precisely analogous to an alkene and, like the latter, can function as a dienophile. The substituent at the central carbon of the allylic cation serves to terminate the reaction. Most often, this substituent is an oxyanion or a silyl ether, but other groups have been used. These (4+3) cycloadditions can proceed via mechanisms that range from stepwise to concerted. Diastereoselectivity, regioselectivity, and enantioselectivity have all been achieved, though there are still opportunities for the development of new reactions in this area. Asymmetric catalysis and enzymatic catalysis of such reactions is in its infancy. More recent advances center on cations that are related to benzylic cations but involve electron rich heterocycles such as furans, indoles, thiophenes and related structures. This chapter covers advances in (4+3) cycloadditions of allylic and related cations from 1997 to 2017, with supplemental references added to bring the work up to date through 2023. It illustrates both the growth in technical progress and theoretical understanding of this reaction during that time.

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Asymmetric Synthesis of Quaternary Stereocenters via Metal Enolates

Korch

Loskot

Stoltz

2017

Patai's Chemistry of Functional Groups

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The strategy of using chiral metal enolate intermediates in a diverse variety of asymmetric transformations has allowed the generation of quaternary stereocenter‐bearing products that are otherwise difficult to access. Many classic transformations including aldol, Mannich, conjugate addition, alkylation, and pericyclic‐type reactions, as well as allylic alkylation and α‐arylation/alkenylation, have been adapted to proceed through chiral metal enolate intermediates, allowing the asymmetric synthesis of many complex products in both an intermolecular and intramolecular manner. These transformations have proven useful in the synthesis of natural products and may also be applied to the synthesis of novel pharmaceuticals and other compounds of interest in the future. This review includes work done up to and including the year 2014.

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Claisen Rearrangement of Aliphatic Allyl Vinyl Ethers from 1912 to 2012: 100 Years of Electrophilic Catalysis

Cited by 59 publications

References 142 publications

Base-Mediated Claisen Rearrangement of CF3-Containing Bisallyl Ethers

Base-Mediated Claisen Rearrangement of CF3-Containing Bisallyl Ethers

(4+3) Cycloadditions of Allylic and Related Cations

Asymmetric Synthesis of Quaternary Stereocenters via Metal Enolates

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