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Further Information

Related Reactions
Ireland-Claisen Rearrangement
Cope Rearrangement
Overman Rearrangement
[2,3]-Wittig Rearrangement

Claisen Rearrangement

The aliphatic Claisen Rearrangement is a [3,3]-sigmatropic rearrangement in which an allyl vinyl ether is converted thermally to an unsaturated carbonyl compound.

The aromatic Claisen Rearrangement is accompanied by a rearomatization:

The etherification of alcohols or phenols and their subsequent Claisen Rearrangement under thermal conditions makes possible an extension of the carbon chain of the molecule.

Mechanism of the Claisen Rearrangement

The Claisen Rearrangement may be viewed as the oxa-variant of the Cope Rearrangement:

Mechanism of the Cope Rearrangement

Mechanism of the Claisen Rearrangement

The reaction proceeds preferably via a chair transition state. Chiral, enantiomerically enriched starting materials give products of high optical purity.

A boat transition state is also possible, and can lead to side products:

The aromatic Claisen Rearrangement is followed by a rearomatization:

When the ortho-position is substituted, rearomatization cannot take place. The allyl group must first undergo a Cope Rearrangement to the para-position before tautomerization is possible.

All Claisen Rearrangement reactions described to date require temperatures of > 100 C if uncatalyzed. The observation that electron withdrawing groups at C-1 of the vinyl moiety exert a positive influence on the reaction rate and the yield has led to the development of the following variations:

Ireland-Claisen Rearrangement

Eschenmoser-Claisen Rearrangement

Johnson-Claisen Rearrangement

Recent Literature

Using Geminal Dicationic Ionic Liquids as Solvents for High-Temperature Organic Reactions
X. Han, D. W. Armstrong, Org. Lett., 2005, 7, 4205-4208.

Base-Mediated Cascade Rearrangements of Aryl-Substituted Diallyl Ethers
J. P. Reid, C. A. McAdam, A. J. S. Johnston, M. N. Grayson, J. M. Goodman, M. J. Cook, J. Org. Chem., 2015, 80, 1472-1498.

Synthesis of γ,δ-Unsaturated Esters and Amides via Au(I)-Catalyzed Reactions of Aryl Ynol Ethers or Ynamides with Allylic Alcohols
S. Misawa, A. Miyairi, Y. Oonoshi, S. P. Nolan, Y. Sato, Synthesis, 2021, 53, 4644-4645.

Base-Mediated Cascade Rearrangements of Aryl-Substituted Diallyl Ethers
J. P. Reid, C. A. McAdam, A. J. S. Johnston, M. N. Grayson, J. M. Goodman, M. J. Cook, J. Org. Chem., 2015, 80, 1472-1498.

Rearrangement of Allyl Homoallyl Ethers to γ,δ-Unsaturated Carbonyl Compounds Catalyzed by Iridium Complexes
T. Higashino, S. Sakaguchi, Y. Ishii, Org. Lett., 2000, 2, 4193-4195.

Stereoselective Olefin Isomerization Leading to Asymmetric Quaternary Carbon Construction
K. Wang, C. J. Bungard, S. G. Nelson, Org. Lett., 2007, 9, 2325-2328.

Tandem Pd(II)-Catalyzed Vinyl Ether Exchange-Claisen Rearrangement as a Facile Approach to γ,δ-Unsaturated Aldehydes
X. Wei, J. C. Lorenz, S. Kapadia, A. Saha, N. Haddad, C. A. Busacca, C. H. Senanayake, J. Org. Chem., 2007, 72, 4250-4253.

A Domino Copper-Catalyzed C-O Coupling-Claisen Rearrangement Process
G. Nordmann, S. L. Buchwald, J. Am. Chem. Soc., 2003, 125, 4978-4979.

Formation of α-Allyl- and Allenyl-Modified Amides via Intermolecular Claisen Rearrangement
Z.-J. Niu, L.-H. Li, X.-S. Li, H.-C. Liu, W.-Y. Shi, Y.-M. Liang, Org. Lett., 2021, 23, 1315-1320.

A Facile Route to Acyclic Substituted α,β-Unsaturated Aldehydes: The Allene Claisen Rearrangement
P. J. Parsons, P. Thomson, A. Taylor, T. Sparks, Org. Lett., 2000, 2, 571-572.

Tandem Horner-Wadsworth-Emmons Olefination/Claisen Rearrangement/Hydrolysis Sequence: Remarkable Acceleration in Water with Microwave Irradiation
E. Quesada, R. J. K. Taylor, Synthesis, 2005, 3193-3195.

Asymmetric Claisen Rearrangements Enabled by Catalytic Asymmetric Di(allyl) Ether Synthesis
S. G. Nelson, K. Wang, J. Am. Chem. Soc., 2006, 128, 4232-4233.

A Convenient Triisobutylaluminium (TIBAL)-Promoted Johnson-Claisen Approach to γ,δ-Unsaturated Alcohols
K. L. Cosgrove, R. P. McGeary, Synlett, 2009, 1749-1752.

Gold(I)-Catalyzed Propargyl Claisen Rearrangement
B. D. Sherry, F. D. Toste, J. Am. Chem. Soc., 2004, 126, 15978-15979.

Stereocontrolled Synthesis of (E,Z)-Dienals via Tandem Rh(I)-Catalyzed Rearrangement of Propargyl Vinyl Ethers
D. V. Vidhani, M. E. Krafft, I. V. Alabugin, Org. Lett., 2013, 15, 4462-4465.

Asymmetric Aza-Claisen Rearrangement between Enantioenriched α-Chiral Allylamines and Allenones
R.-H. Dai, Q. Wang, Z.-X. Chen, S.-K. Tian, J. Org. Chem., 2021, 86, 3065-3073.

A Highly Stereospecific Claisen-Sakurai Approach to Densely Functionalized Cyclopentenols
K. S. Stankevich, M. J. Cook, J. Org. Chem., 2022, 87, 12250-12256.

Synthesis of Pyrroles by Gold(I)-Catalyzed Amino-Claisen Rearrangement of N-Propargyl Enaminone Derivatives
A. Saito, O. Konishi, Y. Hanzawa, Org. Lett., 2010, 12, 372-374.

Gold(I)-Catalyzed Synthesis of Highly Substituted Furans
M. H. Suhre, M. Reif, S. F. Kirsch, Org. Lett., 2005, 7, 3873-3876.

Modular Divergent Synthesis of Functionalized Indoles via TFA-Promoted Amino-Claisen Rearrangement at Room Temperature
Y. Zhang, Y. He, T. Liu, W. Guo, Org. Lett., 2023, 25, 2680-2684.