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.

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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.