Aryl Sulfoxides Research Articles

Asymmetric Synthesis of Alkyl and Aryl Sulfinates of DAG: An Improved and General Route to Both Enantiomerically Pure Sulfoxides

Abstract A short, efficient and general route for the preparation of o.p. alkyl and aryl sulfinates is described. Both epimers at sulfur can be obtained using DAG as unique inductor of chirality and, only by choosing the adequate base (Py or i-Pr2NEt), the configuration at sulfur can be predicted. The efficiency of this methodology has been demonstrated by the synthesis of o.a. alkyl aryl and dialkyl sulfoxides with high e.e. (up to 100%).

Enantiomeric resolution of sulfoxides on a DACH‐DNB chiral stationary phase: A quantitative structure–enantioselective retention relationship (QSERR) study

AbstractThe interaction mechanism of a variety of racemic alkyl aryl sulfoxides with a π‐acid HPLC stationary phase containing N,N′‐(3,5‐dinitrobenzoyl)‐trans‐1,2‐diaminocyclohexane chiral selector was investigated by means of quantum‐chemical calculations (MNDO), partial least squares (PLS) analysis, and 3D comparative molecular field analysis (CoMFA). Quantitative structure–enantioselective retention relationships (QSERR), were derived which have yielded significant insights into physicochemical properties primarily responsible for chiral recognition. The increase in retention (k′) is favored especially by the analyte π‐basic character, accounted for by the sum of the electrophilic superdelocalizabilities of all aromatic carbon atoms (SPhHOMO), and to minor extent by the H‐bond basicity of the sulfoxide oxygen and the hydrophilicity of solutes. In contrast, the separation factor (α) varied mainly with the steric properties of the substituents and with polar and electrostatic properties of the sulfoxide group. A 3D‐QSERR analysis using CoMFA methodology has provided a more complete description of factors responsible for chiral recognition and has proven to be a useful tool to examine differences in noncovalent fields (both the electrostatic and the steric) mostly associated with variations of enantioselectivity. © 1993 Wiley‐Liss, Inc.

A Novel Synthesis Including Asymmetric Synthesis of α,β-Unsaturated γ-Hydroxy Carbonyl Compounds from Enones with Carbon Homologation

Abstract Reaction of the carbanion derived from 1-chloroalkyl aryl sulfoxides with enones gave 1,2-adducts in good yields. Treatment of the adduct with potassium benzenethiolate afforded α-phenylthio β,γ-unsaturated carbonyl compound through an α,β-epoxy sulfoxide. Oxidation of the sulfide with 2.1 equivalents of m-chloroperbenzoic acid gave α,β-unsaturated γ-phenylsulfinyloxy carbonyl compound via sulfoxide-sulfenate rearrangement. The sulfinate was easily hydrolyzed with aqueous potassium hydroxide to afford α,β-unsaturated γ-hydroxy carbonyl compound in good yield. When optically active (−)-1-chloroalkyl p-tolyl sulfoxides were used in this procedure, a synthesis of optically active α,β-unsaturated γ-hydroxy carbonyl compounds with moderate to good optical purity was realized.

1-Haloalkyl Aryl Sulfoxides as Useful Agents in Synthesis of α-Halo Ketones: A New Synthesis of α-Halo Ketones, α-Halo α,β-Unsaturated Ketones, and α-Halo Cross Dienones from Aldehydes

Abstract α-Halo α-sulfinyl ketones were synthesized in two steps from 1-haloalkyl aryl sulfoxides and aldehydes in high yields. Desulfinylation of the α-halo α-sulfinyl ketones was performed with ethylmagnesium bromide in ether at low temperature to afford α-halo ketones via magnesium enolates in high yields. The magnesium enolate intermediates were trapped with various electrophiles such as deuterium oxide, ethyl chloroformate, and chlorotrimethylsilane. Trapping of the magnesium enolate intermediate with carbonyl compounds afforded a new type of the directed aldol reaction. Desulfinylation of the sulfinyl group of the α-halo α-sulfinyl ketones under thermal conditions gave α-halo α,β-unsaturated ketones or α-halo cross dienones.

Optically active sulfoxides by enantiospecific reactions of bromovinyl aryl sulfoxides with grignard reagents

Optically active bromovinyl aryl sulfoxides were subjected to reactions with phenyl- or alkyl-magnesium compounds, with the production of optically active diaryl or aryl alkyl sulfoxides, with inversion of configuration. The enantiospecificity of the process was found to be 98–100%.

The reaction of 2-trimethylsilylethyl sulfoxides with sulfuryl chloride. A fragmentation route to sulfinyl chlorides.

Sulfinyl chlorides were prepared in good to excellent yields by reacting aryl or alkyl 2-trimethylsilylethyl sulfoxides with SO 2Cl 2.

Reactions of 2-halovinyl aryl sulfoxides with organometallic reagents

(E)- and (Z)-2-halovinyl aryl sulfoxides 1-4 were subjected to reactions with organocopper, organomagnesium, or organolithium reagents. The organometallic reagents gave different products: diorganocuprates led to formation of carbon-carbon bond, with production of alkenyl sulfoxides 5-10, whereas formation of carbon-sulfur bond and production of diaryl or aryl alkyl sulfoxides 11-13 were observed in the reaction with the other organometallics. Possible mechanisms for the two observed processes are briefly discussed

A novel synthesis of haloalkenes from aldehydes with carbon-carbon coupling

Treatment of α-halo β-mesyloxy sulfoxides, easily synthesized from aldehydes and 1-haloalkyl aryl sulfoxides in two steps, with n-BuLi at −78 °C gives haloalkenes in good yields.

Lithium-Chlorine Exchange Reaction of α-Chloro α-Sulfonyl Ketones

Abstract Lithium-chlorine exchange of α-chloro α-sulfonyl ketones, easily prepared from 1-chloroalkyl aryl sulfoxides and aldehydes in good yields, with n-butyllithium gave α-sulfonyl ketones in high yields. Some trials to trap the enolate intermediate were carried out.

Recent Developments in Organic Synthesis with 1-Haloalkyl Aryl Sulfoxides

This account deals with recent developments in organic synthesis with 1-haloalkyl aryl sulfoxides, especially with 1-chloroalkyl aryl sulfoxides. 1-Chloroalkyl aryl sulfoxides are quite easily prepared from alkyl aryl sulfides. Sulfinyl carbanions and sulfinylated carbon radicals can easily be generated from 1-chloroalkyl aryl sulfoxides. The sulfinyl carbanions were added to carbonyl compounds to give the adducts, from which various kinds of new carbonyl compounds with carbon homologation were synthesized. Optically active 1-chloroalkyl p-tolyl sulfoxides were obtained from optically active (-)-chloromethyl p-tolyl sulfoxide. Asymmetric syntheses of epoxides, α-amino aldehydes, aziridines, α-hydroxy acids and their derivatives, and propargylic alcohols were realized starting from the optically active (-)-1-chloroalkyl p-tolyl sulfoxides. 1.Introduction 2.Synthesis of 1-Haloalkyl Aryl Sulfoxides 3.Organic Synthesis with 1-Haloalkyl Aryl Sulfoxides 4.Organic Synthesis with Sulfinyloxiranes 4.1.Reaction of Sulfinyloxiranes under Heating or with Lewis Acids 4.2.Reaction of Sulfinyloxiranes with Benzeneselenolate and Thiolates 4.3. Reaction of Sulfinyloxiranes with Amines, Cesium Acetate, and Metal Halides 4.4. Reaction of Sulfinyloxiranes with Alkylmetals 5.Asymmetric Synthesis with Optically Active (-)-1-Chloroalkyl p-Tolyl Sulfoxides 5.1. Preparation of Optically Active Sulfinyloxiranes and a Synthesis of Optically Active Epoxides, α-Amino Aldehydes, and Aziridines 5.2. Asymmetric Synthesis of Both Enantiomers of α-Hydroxy Acids, Esters, Amides, and Propargylic Alcohols 6. Conclusion

Sulfonic Acid-Sodium Iodide System as an Efficient Reagent for the Reduction of Sulfoxides1

A novel deoxygenation of dialkyl, diaryl and alkyl aryl sulfoxides (1) to the corresponding sulfides (2) with a sulfonic acid-sodium iodide system is described (14 examples).

1-クロロアルキルアリルスルホキシドの化学 : カルボニル化合物の新規合成法の開拓と不斉合成への展開

This review deals with novel methods for a homologation of carbonyl compounds by using 1-chloroalkyl aryl sulfoxides as acyl anion equivalents. The products obtained from these methods are those of dialkyl ketones, aldehydes, α-substituted carbonyl compounds, vinyl-and divinyl ketones, 1-acylbutadienes, α, β-unsaturated carbonyl compounds, aldols, epoxides, allylic alcohols, (Z)-N-arylaziridines, and α-hydroxycarboxylic acids and their derivatives. Novel synthetic methods for cyclic ketones or new annulation procedures were achieved by using these new procedures. As the novel methods for asymmetric synthesis, a practical procedure for preparing optically pure 1-chloroalkyl p-tolyl sulfoxides was achieved. Optically active epoxides, (Z)-N-arylaziridines, α-amino aldehydes, and α-hydroxycarboxylic acids and their derivatives were synthesized from carbonyl compounds or imines and the optically active 1-chloroalkyl p-tolyl sulfoxides.

Mild and Efficient Deoxygenation of Sulfoxides with Titanium(IV) Chloride/Sodium Iodide Reagent System

Dialkyl, diaryl and alkyl aryl sulfoxides were readily deoxygenated to the corresponding sulfides in excellent yields with titanium(IV) chloride/sodium iodide reagent system at room temperature.

ChemInform Abstract: A New Synthesis of β‐Keto Sulfoxides from Chloromethyl Aryl Sulfoxide and Aldehydes.

ChemInformVolume 21, Issue 36 Preparative Organic Chemistry ChemInform Abstract: A New Synthesis of β-Keto Sulfoxides from Chloromethyl Aryl Sulfoxide and Aldehydes. T. SATOH, T. SATOH Fac. Pharm. Sci., Sci. Univ. Tokyo, Shinjuku, Tokyo 162Search for more papers by this authorT. FUJII, T. FUJII Fac. Pharm. Sci., Sci. Univ. Tokyo, Shinjuku, Tokyo 162Search for more papers by this authorK. YAMAKAWA, K. YAMAKAWA Fac. Pharm. Sci., Sci. Univ. Tokyo, Shinjuku, Tokyo 162Search for more papers by this author T. SATOH, T. SATOH Fac. Pharm. Sci., Sci. Univ. Tokyo, Shinjuku, Tokyo 162Search for more papers by this authorT. FUJII, T. FUJII Fac. Pharm. Sci., Sci. Univ. Tokyo, Shinjuku, Tokyo 162Search for more papers by this authorK. YAMAKAWA, K. YAMAKAWA Fac. Pharm. Sci., Sci. Univ. Tokyo, Shinjuku, Tokyo 162Search for more papers by this author First published: September 4, 1990 https://doi.org/10.1002/chin.199036112Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume21, Issue36September 4, 1990 RelatedInformation

ChemInform Abstract: Pyrolysis of α‐Acyl‐Substituted Ethyl Phenyl Sulfoxides.

AbstractEthyl aryl sulfoxides such as (I) and (IV) are pyrolyzed, yielding the corresponding alkenes (II) and (V), together with the sulfenic acids (III).

A New Synthesis of β-Keto Sulfoxides from Chloromethyl Aryl Sulfoxide and Aldehydes

Abstract Addition of the carbanion of chloromethyl aryl sulfoxide to aldehyde gave the adduct, which was treated with three-equivalents of lithium diisopropylamide (LDA) to afford β-keto sulfoxide in high overall yield.

Facile Synthesis of α-Chlorosulfoxide Using the N,N′-Dichloro-p-toluenesulfonamide

Abstract Various unsymmetrical and symmetrical diakyl sulfoxides or alkyl aryl sulfoxides reacted with N,N′-dichloro-p-toluenesulfonamide to yield the corresponding α-chlorosulfoxide in excellent yields under mild and neutral conditions in high regioselectivity of monochlorination at α-position of sulfoxides.

Preparation and rearrangement of 2-allyloxyethyl aryl sulfoxides; a mercury-free claisen sequence

Alkali metal hydride promoted addition of allylic alcohols to aryl vinyl sulfoxides at room temperature gives 2-allyloxyethyl aryl sulfoxides, which, on heating, are converted into γ,δ-unsaturated aldehydes via allylic vinyl ethers.

ChemInform Abstract: Acetylenic Sulfoxides in Organic Synthesis: Diels‐Alder Reactions.

AbstractThe alkynyl aryl sulfoxides (VII), prepared from p‐nitrothiophenol (I) as shown in the reaction scheme, undergo Diels‐Alder reaction with cyclopentadiene (VIII), 2,3‐dimethylbuta‐1,3‐diene (X), or anthracene (XII) to give the cycloadducts (IX), (XI), and (XIII).

ChemInform Abstract: Ligand Coupling Through σ‐Sulfurane. Complete Retention of Geometric Configuration of Allylic and Vinylic Groups in the Reactions of Allylic and Vinylic Sulfoxides with Grignard Reagents.

Abstract(Het)aryl sulfoxides, e.g. the compounds (I), are treated with various Grignard agents such as (II), (V), and (VIII) to yield desulfonated or coupling products.