Facial selectivity of the Ireland–Claisen rearrangement of allylic esters of 2-methyl and 2-methoxycyclopentanecarboxylic acids

Gilbert, John; Yin, Jiandong; Fakhreddine, Fatima H.; Karpinski, Matthew L.

doi:10.1016/j.tet.2003.11.002

Cited by 13 publications

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“…2 This method involves silylene transfer to an R,β-unsaturated ester, providing a silyl ketene acetal with complete regio-and stereoselectivity. When transfer to an R,β-unsaturated allylic ester occurs, the resulting silyl ketene acetal can undergo a stereospecific Ireland-Claisen rearrangement 3,4 with high facial selectivity 5 to provide silalactone products possessing a quaternary carbon stereocenter (eq 1).…”

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“…6 The formation of new stereocenters in the silylene transfer/ Ireland-Claisen rearrangement can be controlled by a stereocenter at the allylic position of an R,β-unsaturated allylic ester. 7,8 likely occurred by formation of a silacarbonyl ylide (5), which then underwent a 6π electrocyclization to provide oxasilacyclopentene 6 (Scheme 1). This intermediate contains a tetrasubstituted silyl ketene acetal moiety embedded within the ring.…”

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Formation of Chiral Quaternary Carbon Stereocenters Using Silylene Transfer Reactions: Enantioselective Synthesis of (+)-5-epi-Acetomycin

Calad

Woerpel

2007

Org. Lett.

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Formation of Chiral Quaternary Carbon Stereocenters Using Silylene Transfer Reactions: Enantioselective Synthesis of (+)-5-epi-Acetomycin

Calad

Woerpel

2007

Org. Lett.

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Claisen Rearrangement

2010

Comprehensive Organic Name Reactions and Reagents

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Thermal isomerization of an allyl vinyl ether or of its nitrogen‐ or sulfur‐containing analogous derivatives to afford a bifunctionalized molecule in a [π2a + σ2s + π2s] process is known as the Claisen rearrangement. This reaction is a highly stereoselective [3,3]‐sigmatropic rearrangement of allyl vinyl or allyl aryl ethers to yield γ,δ‐unsaturated carbonyl compounds or o ‐allyl substituted phenols, respectively. In most cases, the reaction has been found to proceed preferably via a chair‐like transition state, and chiral, enantiomerically enriched starting materials give products of highly optical purity. This rearrangement is found to run faster in a polar solvent. The microwave irradiation can also accelerate the reaction rate. It is also found that substituents on allyl vinyl ether play important roles on the reactivity of corresponding allyl vinyl ethers and these modifications lead to more than 20 variations of the traditional Claisen rearrangement. This reaction, along with its various modifications, has wide applications in organic synthesis.

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Facial Selectivity of the Ireland—Claisen Rearrangement of Allylic Esters of 2‐Methyl and 2‐Methoxycyclopentanecarboxylic Acids.

et al. 2004

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Facial Selectivity of the Ireland-Claisen Rearrangement of Allylic Esters of 2-Methyl and 2-Methoxycyclopentanecarboxylic Acids. -The stereoselectivity of the Ireland-Claisen rearrangement of 2-methyl and 2-methoxy substituted cyclopentane-carboxylate systems is investigated. The studies reveal that the 2-methyl-substituted systems rearrange with complete facial selectivity at the ring position, but the (Z)-or (E)-crotyl systems give a mixture of diastereomers. In contrast, a 2-methoxy group in the five-membered ring system (VI) does not control the diastereoselectivity. -(GILBERT*, J. C.; YIN, J.; FAKHREDDINE, F. H.; KARPINSKI, M. L.; Tetrahedron 60 (2004) 1, 51-60; Dep. Chem. Biochem., Univ. Tex., Austin, TX 78712, USA; Eng.) -Bartels 20-061

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Facial selectivity of the Ireland–Claisen rearrangement of allylic esters of 2-methyl and 2-methoxycyclopentanecarboxylic acids

Cited by 13 publications

References 25 publications

Formation of Chiral Quaternary Carbon Stereocenters Using Silylene Transfer Reactions: Enantioselective Synthesis of (+)-5-epi-Acetomycin

Formation of Chiral Quaternary Carbon Stereocenters Using Silylene Transfer Reactions: Enantioselective Synthesis of (+)-5-epi-Acetomycin

Claisen Rearrangement

Facial Selectivity of the Ireland—Claisen Rearrangement of Allylic Esters of 2‐Methyl and 2‐Methoxycyclopentanecarboxylic Acids.

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