Chiral homoallylic and allylic sulfoxides as models for the stereochemical analysis of sulfoxide thiaoleates

Daligault, Franck; Arboré, Amélie; Nugier‐Chauvin, Caroline; Patin, Henri

doi:10.1016/j.tetasy.2004.01.018

Cited by 12 publications

(5 citation statements)

References 28 publications

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“…The absolute configuration of the sulfinates was confirmed by a comparison of the chiroptical and NMR data (characteristic 1 H resonances (H2) and 13 C resonances (C1-C4) for these compounds with that of literature values reported for the two diastereomeric DAG n-propylsulfinates 16 and DAG n-butylsulfinates. 17 Treatment of DAG-(S)-or (R)-w-fluorooctanesulfinates with 3 equivalents of 8-OTBS-1-nonylmagnesium bromide yielded, after deprotection, enantiomerically enriched samples of (R)-and (S)-1 respectively. This substitution reaction is known to proceed with inversion of configuration at the sulfinyl centre of the DAG-alkylsulfinates.…”

Section: Resultsmentioning

confidence: 99%

Stereochemistry of 10-sulfoxidation catalyzed by a soluble Δ9 desaturase

et al. 2010

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The stereochemistry of castor stearoyl-ACP Delta(9) desaturase-mediated 10-sulfoxidation has been determined. This was accomplished by (19)F NMR analysis of a fluorine-tagged product, 18-fluoro-10-thiastearoyl ACP S-oxide, in combination with a chiral solvating agent, (R)-AMA. Sulfoxidation proceeds with the same stereoselectivity as hydrogen removal from the parent stearoyl substrate. These data validate the use of thia probes to determine the stereochemistry and cryptoregiochemistry of desaturase-mediated oxidations.

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Section: Resultsmentioning

confidence: 99%

Stereochemistry of 10-sulfoxidation catalyzed by a soluble Δ9 desaturase

et al. 2010

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“…Further conversions allowed the formation of the sulfoxide 78 , which was considered as a chiral fragment of the antibiotic ( S )-sparsomycin. A diacetone−glucose auxiliary was also used in the synthesis of the ( R )- and ( S )-enantiomers of allylic and homoallylic sulfoxides 79 and 80 . , These derivatives, which served as models in the investigation of the mechanism of oleic acid desaturation, were obtained in 66−84% yield and 96% ee .…”

Section: Chemical Methods Of Nonracemic Sulfoxide Preparationmentioning

confidence: 99%

“…A diacetone-glucose auxiliary was also used in the synthesis of the (R)-and (S)enantiomers of allylic and homoallylic sulfoxides 79 and 80. 148,149 These derivatives, which served as models in the investigation of the mechanism of oleic acid desaturation, were obtained in 66-84% yield and 96% ee.…”

Section: Chiral Sulfinate Methodsmentioning

confidence: 99%

“…Chiral hydroperoxides were used not only in titanium-catalyzed sulfoxidations (see section 1.4.3.1.1) [221][222][223][224][225] but also in metal-free oxidations of prochiral sulfides. Aoki and Seebach prepared a stable, crystalline hydroperoxy alcohol, TADOOH (149). 226 Thioanisole was oxidized by TADOOH without any catalysts in THF solution to produce mainly the (S)-sulfoxide in 73% yield and 86% ee under optimized conditions (1.5 equiv of oxidant, 96 h, -30 °C f RT).…”

Section: C-s Bond Formationmentioning

confidence: 99%

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Enantioselective Synthesis of Sulfoxides: 2000−2009

2010

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Elz ˙bieta Wojaczyn ´ska (ne ´e Ostrycharz) was born in Z ˙migród, Poland. She received her M.Sc. degree in organic chemistry from Wrocław University of Technology in 1997. Her doctoral thesis on the enantioselective synthesis and application of chiral sulfoxides was completed under the supervision of Professor Jacek Skarz ˙ewski in 2001. Her research at the Department of Organic Chemistry of the Wrocław University of Technology focuses on the synthesis of new chiral building blocks and of novel chiral ligands for the asymmetric synthesis. Jacek Wojaczyn ´ski was born in Wrocław in 1969. He graduated from the University of Wrocław in inorganic chemistry in 1993. He received his Ph.D. in 1998 for work on the influence of asymmetric modification of the porphyrin periphery on the properties of formed complexes. He is a member of the Porphyrin Chemistry Research Group led by Professor Lechosław Latos-Graz ˙yn ´ski at the Department of Chemistry, University of Wrocław. His current scientific interests include degradation of tetrapyrrolic macrocycles and investigation of paramagnetic hemoproteins using NMR spectroscopy.

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“…Finally, chiral sulfinate esters such as diacetone- d -glucose (DAG) or menthyl derivatives are among the more frequent precursors of all kinds of sulfoxides and are also useful for accessing enantiomerically enriched allylic sulfoxides by reaction with Grignard or lithium reagents. An interesting related approach developed by Vogel and Turks and co-workers , is based on the sila- and bora-ene reactions of allylsilane and allylborane derivatives 80 and 81 with SO 2 , which allows for the synthesis of allylic sulfinates 82 and 83 (Scheme ).…”

Section: Synthesis Of Allylic Sulfoxidesmentioning

confidence: 99%

From Allylic Sulfoxides to Allylic Sulfenates: Fifty Years of a Never-Ending [2,3]-Sigmatropic Rearrangement

et al. 2017

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The [2,3]-sigmatropic rearrangement of allylic sulfoxides to allylic sulfenates is a reversible process, generally shifted toward the sulfoxide. In the presence of thiophiles, the sulfenate is trapped, and allylic alcohols are obtained under mild conditions. In most cases, a good transfer of stereochemical information through an ordered transition state is obtained. Furthermore, the ease of coupling this process with other versatile, stereocontrolled reactions has enhanced the usefulness of this protocol. This review aims to provide a comprehensive survey of this rearrangement and its application in the synthesis of natural and bioactive products.

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Chiral homoallylic and allylic sulfoxides as models for the stereochemical analysis of sulfoxide thiaoleates

Cited by 12 publications

References 28 publications

Stereochemistry of 10-sulfoxidation catalyzed by a soluble Δ9 desaturase

Stereochemistry of 10-sulfoxidation catalyzed by a soluble Δ9 desaturase

Enantioselective Synthesis of Sulfoxides: 2000−2009

From Allylic Sulfoxides to Allylic Sulfenates: Fifty Years of a Never-Ending [2,3]-Sigmatropic Rearrangement

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