49833-45-6

Upstream product

• 594-19-4 tert.-butyl lithium 
• 4820-07-9 benzyl p-tolyl sulfoxide 
• 1858-86-2 Ethyl p-toluenesulfinate 
• 677-22-5 tert-butylmagnesium chloride 
• 7439-10-3 tert-butyl 4-methylphenyl sulfide 
• 77096-69-6 1-benzenesulfinyl-4-methyl-benzene 
• 13146-08-2 Toluol-4-sulfinsaeure-neopentylester 
• 672-78-6 methyl p-toluene sulfinate 
• 23730-26-9 tert-butyl 4-methylbenzenesulfinate 
• 33692-24-9 N-Methyl-N-phenyl-p-toluolsulfinamid 
• 31536-21-7 isopropyl 4-methylbenzenesulfinate 
• 136378-30-8 2-(p-tolylsulfinyl)naphthalene 
• 20268-16-0 (R)-(+)-2-chlorophenyl 4-methylphenyl sulfoxide 
• 16491-20-6 (R)-1-methyl-4-(phenylsulfinyl)benzene 

Downstream Products

• 7439-10-3 tert-butyl 4-methylphenyl sulfide 
• 77096-69-6 1-benzenesulfinyl-4-methyl-benzene 
• 53040-92-9 4-(4-tolyl)anisole 
• 620-93-9 di-p-tolylamine 

Relevant academic research and scientific papers

One-Pot Sulfoxide Synthesis Exploiting a Sulfinyl-Dication Equivalent Generated from a DABSO/Trimethylsilyl Chloride Sequence

A one-pot process for the synthesis of unsymmetrical sulfoxides using organometallic nucleophiles is described. Sulfur dioxide, delivered from the surrogate DABSO (DABCO-bis(sulfur dioxide)), acts as the initial electrophile and combines with the first organometallic reagent to generate a sulfinate intermediate. In situ conversion of the sulfinate to a sulfinate silyl ester, using TMS-Cl (trimethylsilyl chloride), generates a second electrophile, allowing addition of a second organometallic reagent. Organolithium or Grignard reagents can be employed, delivering sulfoxides in good to excellent yields.

Tert-Butyl Sulfoxides: Key Precursors for Palladium-Catalyzed Arylation of Sulfenate Salts

The present report describes an efficient and clean generation of sulfenate salts (R1SO-) by pyrolysis of readily available tert-butyl sulfoxides to give sulfenic acids (R1SOH) and traceless isobutene, followed by hydrogen abstraction with a weak inorganic base (K3PO4). The relevance of this process was exemplified through an in situ palladium-catalyzed cross-coupling reaction with aryl halides/triflates leading to aryl sulfoxides. The operationally simple C-S bond-forming protocol developed uses Pd(dba)2 as catalyst and Xantphos as ligand in toluene or a toluene/H2O mixture. Further extensions include the use of di-tert-butyl sulfoxide as an equivalent for sulfur monoxide dianion (SO2-) and the development of diastereoselective versions in the [2.2]paracyclophane and biaryl series.

Diastereoconvergent synthesis of trans -5-hydroxy-6-substituted-2- piperidinones by addition-cyclization-deprotection process

A diastereoselective one-pot approach to access trans-5-hydroxy-6- substituted-2-piperidinones by an addition-cyclization-deprotection process has been developed, in which the stereogenic center at the C-6 position was solely controlled by α-OTBS group. The utility of this transformation is demonstrated by the asymmetric synthesis of the enantiomer of (-)-CP-99,994.

Structural effects on the C-S bond cleavage in aryl tert -butyl sulfoxide radical cations

The oxidation of a series of aryl tert-butyl sulfoxides (4-X-C 6H4SOC(CH3)3: 1, X = OCH 3; 2, X = CH3; 3, X = H; 4, X = Br) photosensitized by 3-cyano-N-methylquinolinium perchlorate (3-CN-NMQ+) has been investigated by steady-state irradiation and nanosecond laser flash photolysis (LFP) under nitrogen in MeCN. Products deriving from the C-S bond cleavage in the radical cations 1+?-4+? have been observed in the steady-state photolysis experiments. By laser irradiation, the formation of 3-CN-NMQ? (λmax = 390 nm) and 1 +?-4+? (λmax = 500-620 nm) was observed. A first-order decay of the sulfoxide radical cations, attributable to C-S bond cleavage, was observed with fragmentation rate constants (k f) that decrease by increasing the electron donating power of the arylsulfinyl substituent from 1.8 × 106 s-1 (4 +?) to 2.3 × 105 s-1 (1 +?). DFT calculations showed that a significant fraction of the charge is delocalized in the tert-butyl group of the radical cations, thus explaining the small substituent effect on the C-S bond cleavage rate constants. Via application of the Marcus equation to the kinetic data, a very large value for the reorganization energy (λ = 62 kcal mol-1) has been calculated for the C-S bond scission reaction in 1+?-4 +?.

The synthesis of enantiomerically pure 4-substituted [2.2]paracyclophane derivatives by sulfoxide-metal exchange

A general strategy for the synthesis of enantiomerically pure 4-substituted [2.2]paracyclophanes from a common sulfoxide precursor is described. The Royal Society of Chemistry 2005.

Nucleophilic epoxidation of α′-hydroxy vinyl sulfoxides

The nucleophilic epoxidation of a variety of α′-(1-hydroxyalkyl) vinyl sulfones and sulfoxides has been studied. The sulfones give rise to anti oxiranes with modest (E) or excellent (Z) selectivities and in good yields. The (E)-sulfoxides display low reactivity within a reinforcing/nonreinforcing scenario. The use of t-BuOOLi in Et2O allows for a highly syn-selective epoxidation-oxidation. The (Z)-sulfoxides display a remarkably high reactivity under these conditions. The reinforcing (S,Ss) diastereomers (3e-g) yield hydroxy sulfinyl oxiranes with high yields and selectivities. In contrast, the (R,Ss) diastereomers (4e-g) show diminished reactivities and a very substrate-dependent stereochemical outcome. The structure of these oxiranes has been secured by chemical correlations and an X-ray crystal structure.

Generation of oxiranyllithiums and oxiranyl Grignard reagents having a carbanion-destabilizing group from sulfinyloxiranes: Their property and an application to asymmetric synthesis of epoxides and alcohols

The first generation of oxiranyllithiums and oxiranyl Grignard reagents having a carbanion-destabilizing group (alkyl group) was realized from sulfinyloxiranes via the ligand exchange reaction of sulfoxides with tert- butyllithium or ethylmagnesium chlori

Titanium-Catalyzed, Asymmetric Sulfoxidation of Alkyl Aryl Sulfides with Optically Active Hydroperoxides

The Ti-catalyzed, asymmetric oxidation of alkyl aryl sulfides by enantiomerically pure hydroperoxides (ee >99%) has been examined. Enantioselectivities with ee values up to ca. 80% were achieved for the oxygen transfer from (S)-(-)-1-phenylethyl hydroperoxide 2a to methyl phenyl and methyl p-tolyl sulfide 1a in CCl4 as solvent, but with much overoxidation to the corresponding sulfone 4. Detailed mechanistic studies showed that the enantioselectivity of the sulfide 1a oxidation results from a combination of a rather low (ee values >20%) asymmetric induction in the sulfoxidation and an effective kinetic resolution (ee values ca. 80% at 85% sulfide conversion) of the sulfoxide 3a by enantioselective oxidation to the sulfone 4a. The overoxidation (loss of chemoselectivity) is due to sulfoxide coordination to the Ti metal to generate a template in which the oxygen atom is intramolecularly transferred from the bound and activated, optically active hydroperoxide to the ligated sulfoxide in a stereocontrolled manner.

Extremely Facile Ligand-Exchange and Disproportionation Reactions of Diaryl Sulfoxides, Selenoxides, and Triarylphosphine Oxides with Organolithium and Grignard Reagents

Diaryl sulfoxides undergo unusually rapid ligand-exchange reaction upon treatment with organolithium reagents at -95 deg C.Optically pure phenyl p-tolyl sulfoxide (4b) reacted with organolithium reagents at the range from -20 to -95 deg C to give facile ligand-exchange and disproportionation products, i.e., diphenyl sulfoxide (7), recovered 4b, and di-p-tolyl sulfoxide (8) in a statistical ratio of 1:2:1 in quantitative yields, and the recovered 4b was completely racemized.This facile ligand exchange was observed in the similar reactions using only diaryl selenoxides and triarylphosphine oxides.The reactions of 18O-labeled phenyl p-tolyl sulfoxide (4c) with organolithium reagents gave products in a statistical ration without 18O scrambling, indicating that only the C-S bond cleavage took place under low temperature.It is suggested that the ligand exchange reactions occur by the nucleophilic attack by organolithium reagent at the sulfinyl sulfur atom, giving ?-sulfurane as an intermediate that collapses rapidly.These results suggest that the treatment of arylic sulfoxides, selenoxides, and phosphine oxides with strong bases should be effected with caution.

ORGANOSULPHUR COMPOUNDS-LXIX OPTICALLY ACTIVE SULPHINATES: A NEW TYPE OF ENANTIOSELECTIVE ASYMMETRIC SYNTHESIS AND KINETIC RESOLUTION

Optically active sulphinates with the sulphur atom as a sole centre of chirality are prepared by two methods.The first involves the reaction of symmetrical sulphites with tert-butylmagnesium chloride in the presence of optically active aminoalcohols.This new asymmetric, enantioselective synthesis affords t-butylsulphinates with 40-70percent enantiomeric excess values.The second approach is based on a new type of kinetic resolution taking place when racemic sulphinates are reacted with tert-butylmagnesium chloride complexed by optically active alkaloid bases.Both the recovered sulphinates and sulphoxides formed in this reaction show moderate optical purities.