The thermal, aliphatic Claisen rearrangement

Ziegler, Frederick E.

doi:10.1021/cr00090a001

Cited by 518 publications

(238 citation statements)

References 31 publications

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“…[5a,b] It has been tentatively suggested [1c] that a second oxo group, which serves as a spectator ligand, could help to stabilize the negative charge developed on the metal in the transition state, thereby lowering the activation barrier. It was also suggested, [1c] in line with the known mechanistic data on the Claisen rearrangement, [6] that in the catalyzed isomerization of A the greater activation enthalpy for the formation of the cis isomer C might be accounted for by a greater difference in charge and/or separation (distance effect) in the corresponding transition state. This increase in charge separation, which would correspond to a quasi-ionic pair TS, would also be consistent with the unexpected observation of a positive entropy of activation.…”

Section: Tsmentioning

confidence: 83%

Mechanism of the Allylic Rearrangement of Allyloxo Metal Oxo Complexes: An Ab Initio Theoretical Investigation

Bellemin‐Laponnaz

Dedieu

1999

Chem. Eur. J.

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The mechanism of the isomerization of allyl alcohols by the 1,3-transposition of a hydroxy group, which is catalyzed by transition metal complexes in a high oxidation state, has been investigated by ab initio quantum chemical calculations for a trioxorhenium catalyst. The calculations point to a cyclic transition state that consists of a perrhenate anionic moiety and an allylic cationic group. This is similar to the transition state found for the [3,3] sigmatropic rearrangement in allyl formate. The energy barrier is lower in the organometallic case. The calculations also suggest that the kinetic discrimination that is observed experimentally for the catalyzed cis ± trans isomerization of hex-1-en-3-ol is due to microsolvation effects of the corresponding transition states by the alcohols that are present in the reaction medium. All these features are explained in terms of orbital interactions present in the transition state.

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Section: Tsmentioning

confidence: 83%

Mechanism of the Allylic Rearrangement of Allyloxo Metal Oxo Complexes: An Ab Initio Theoretical Investigation

Bellemin‐Laponnaz

Dedieu

1999

Chem. Eur. J.

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“…The resulting cyclic oxonium ion 2 has a structural platform for a [3,3]-sigmatropic rearrangement, which generates cycloheptenyl cation 3. [4] Elimination of the cationic metal species produces 1-alkoxy-1,4-cycloheptadiene 4 in a catalytic manner.…”

mentioning

confidence: 99%

Gold(I)‐Catalyzed Cycloisomerization of 3‐Methoxy‐1,6‐enynes Featuring Tandem Cyclization and [3,3]‐Sigmatropic Rearrangement

et al. 2008

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Golden reactivity: A new gold(I)‐catalyzed cycloisomerization of 3‐methoxy‐1,6‐enynes was discovered. Structurally simple 3‐methoxy‐1,6‐enynes engage in a tandem cyclization/[3,3]‐sigmatropic rearrangement to deliver a variety of 1‐methoxy‐1,4‐cycloheptadienes (see scheme). Notably, the reaction can be performed under very mild conditions and the synthetic utility of this reaction was demonstrated by facile conversion of the product into various cyclohept‐4‐en‐1‐ones.

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“…In view of the applicability in organic synthesis, the protocol offers an alternative to Claisen rearrangement routes to , -unsaturated esters from allylic alcohols. 13 Mild reaction conditions and the resulting broad functional group compatibility would be benefits of using the present coppercatalyzed method.…”

Section: Phmentioning

confidence: 94%

Efficient Preparation of β-Branched γ,δ-Unsaturated Esters through Copper-Catalyzed Allylic Alkylation of Ketene Silyl Acetal

Liu¹,

Ohmiya²,

Sawamura³

2012

Synthesis

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Abstract:Copper-catalyzed allylic alkylation of ketene silyl acetals proceeded with excellent -E-selectivity. Efficient -to-chirality transfer with anti-selectivity occurred in the reaction of enantioenriched secondary allylic phosphates, affording enantioenrichedbranched , -unsaturated esters. The reaction was readily scalable and highly reliable in terms of product yield and stereoselectivities.

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The thermal, aliphatic Claisen rearrangement

Cited by 518 publications

References 31 publications

Mechanism of the Allylic Rearrangement of Allyloxo Metal Oxo Complexes: An Ab Initio Theoretical Investigation

Mechanism of the Allylic Rearrangement of Allyloxo Metal Oxo Complexes: An Ab Initio Theoretical Investigation

Gold(I)‐Catalyzed Cycloisomerization of 3‐Methoxy‐1,6‐enynes Featuring Tandem Cyclization and [3,3]‐Sigmatropic Rearrangement

Efficient Preparation of β-Branched γ,δ-Unsaturated Esters through Copper-Catalyzed Allylic Alkylation of Ketene Silyl Acetal

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