Stereoselective Synthesis of Cyclopropanes via Homoallylic Participation

Nagasawa, Tetsuya; Handa, Y.; Onoguchi, Yuka; Ohba, Shigeru; Suzuki, Keisuke

doi:10.1055/s-1995-5071

Cited by 31 publications

(9 citation statements)

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“…In practical terms, the cyclization of 89 was both fast and efficient, 47 although not as stereoselective as we had hoped. Exposure of 89 to trifluoromethanesulfonic anhydride at low temperature led in quantitative yield to just two products, cyclopropanes 90 and 91 in the ratio 7.6:1 (Scheme 16).…”

Section: A Ring-closing Metathesis Approach To the Octenalactone Portion Of Solandelactonesmentioning

confidence: 75%

Strategies for the Synthesis of the Cyclopropyl-Substituted Lactone Family of Oxylipins

White¹,

Yang²

2009

Synlett

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Biomimetic and other strategies that have been developed in the author's laboratory for the synthesis of a subset of the group of enzymically oxidized lipids known as oxylipins are described. This set of oxylipins contains both a cyclopropane and a lactone, with the lactone ring size varying between six and nine members. A biomimetic approach employing cascade cyclization of an epoxyalkenoic acid was successful in creating the cyclopropane and six-membered lactone of C 20 oxylipins such as the constanolactones in a single step, but failed in an attempt to create the ninemembered lactone of halicholactone. Solandelactones, C 22 oxylipins containing a cyclopropane and an eight-membered lactone, were synthesized by directed Simmons-Smith cyclopropanation followed by Claisen rearrangement of a cyclic ketene acetal to construct the lactone

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Section: A Ring-closing Metathesis Approach To the Octenalactone Portion Of Solandelactonesmentioning

confidence: 75%

Strategies for the Synthesis of the Cyclopropyl-Substituted Lactone Family of Oxylipins

White¹,

Yang²

2009

Synlett

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“…While the fate of the homoallylic cation can be difficult to control, methods to accomplish cyclopropanation in this way have been developed. Suzuki found that the electron‐rich nature of trisubstituted olefins precludes the rearrangements normally associated with homoallylic cations [Figure 1, Equation (1)] 10a. Building on this, Taylor reported that by functionalizing the alkene with a β‐silyl substituent, one could trap the transient cyclopropylcarbinyl intermediate via rapid β‐silyl elimination following a concerted (i.e.…”

Section: Scope Of the Cationic Cyclization Reaction[a][b][c][d][e][fmentioning

confidence: 99%

Synthesis of Perfluoroalkyl‐Substituted Vinylcyclopropanes by Way of Enhanced Neighboring Group Participation

et al. 2015

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A simple, high yielding, two‐step, one‐pot protocol for the preparation of trifluoromethyl‐substituted vinylcyclopropanes from α‐CF3 homoallyl alcohols is disclosed. Destabilization of the cationic intermediate by the electron‐withdrawing CF3 group greatly enhances neighboring group participation of the alkene, allowing ring closure to predominate. The reaction can be extended to the difluoromethyl and pentafluoroethyl group, enabling the preparation of a diverse array of fluoroalkyl‐substituted vinylcyclopropanes.

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“…Exposure of alcohols (M, M′) to trifluoromethanesulfonic anhydride (Tf 2 O) followed by a trimethylamine quench provided exclusively the trans-vinylcyclopropanes(N,N′) in good yield. The facile method for synthesizing trans-di-substituted cyclopropane was reviewed by Japanese researchers in 1996 (88).…”

Section: Newer Approaches To Lipids Synthesis Via C-3 Synthetic Buildmentioning

confidence: 99%

Newer synthetic approaches to surfactants, lipids, and related compounds based on C‐3 building blocks: Recent advances related to fatty chemistry

Urata

Takaishi

1999

J Surfact & Detergents

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Many lipids derived from natural sources are based on the glycerin molecule. Synthetically alkyl glycidyl ether can be used as a C‐3 building block for lipid molecules as well as alkyl glyceryl ether. Several glycidyl and glyceryl ethers have been studied as C‐3 synthetic building blocks for lipids used in surfactants/emulsifiers, cosmetics, or toiletries. From an environmental viewpoint, several surfactants and detergents have been modified by using epichlorohydrin or glycerides as C‐3 building blocks to have higher performance or biodegradability. Recently, complex lipid molecules having special bioactivities have attracted attention among chemists. Glycidyl ether would be expected to be one of the synthetic building blocks for such complex lipids.

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Stereoselective Synthesis of Cyclopropanes via Homoallylic Participation

Cited by 31 publications

References 0 publications

Strategies for the Synthesis of the Cyclopropyl-Substituted Lactone Family of Oxylipins

Strategies for the Synthesis of the Cyclopropyl-Substituted Lactone Family of Oxylipins

Synthesis of Perfluoroalkyl‐Substituted Vinylcyclopropanes by Way of Enhanced Neighboring Group Participation

Newer synthetic approaches to surfactants, lipids, and related compounds based on C‐3 building blocks: Recent advances related to fatty chemistry

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