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Synfacts 2022; 18(05): 0527
DOI: 10.1055/s-0041-1738040
Metals in Synthesis

The Enantioselective Overman Rearrangement

Contributor(s):
Martin Oestreich
,
Hendrik F. T. Klare
,
Benedikt Wolff
Anderson CE, Overman LE. * University of California, Irvine, USA
Catalytic Asymmetric Rearrangement of Allylic Trichloroacetamidates. A Practical Method for Preparing Allylic Amines and Congeners of High Enantiomeric Purity.

J. Am. Chem. Soc. 2003;
125: 12412-12413
DOI: 10.1021/ja037086r.
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Key words

allylic alcohols - allylic amines - acetamidates - palladium catalysis - [3+3]-sigmatropic rearrangement

Significance

Although first reported in 1974 (J. Am. Chem. Soc. 1974, 96, 597), an enantioselective variant of the Overman rearrangement remained challenging for the following decades. Competing elimination reactions, slow reaction rates, and low enantioselectivities were overcome by using the dimeric palladium catalyst COP-Cl. Starting from allylic alcohols, allylic amides are accessible in two steps with a formal [3+3]-sigmatropic rearrangement as the key step.


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Comment

High enantioselectivities and yields were observed throughout. Only sterically demanding substituents and aryl groups revealed the limitation of this protocol. The potential of this method was further demonstrated by derivatization of the obtained allylic amides, e.g., providing unnatural amino acids in only a few steps. Aside from palladium, mercury-, platinum- and gold-based catalysts have also been disclosed (for a review, see: Org. Biomol. Chem. 2017, 15, 2672).


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Publication History

Article published online:
20 April 2022

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