33957-73-2

Upstream product

• 41924-26-9 bis((trimethylsilyl)methyl)zinc 
• 104173-06-0 C₁₈H₂₇NOS 
• 17246-91-2 N¹,N¹,N²-Trimethyl-benzolsulfonamidin 
• 616234-10-7 (+)-(E,S_S,2S,3R)-5-[N-methyl-S-phenylsulfonimidoyl]-3-methyl-2-[(2-methylprop-2-ylsulfonyl)-prop-2-ynylamino]-pent-4-enoic acid ethyl ester 
• 616234-11-8 (+)-(E,S_S,2S,3R)-5-[N-methyl-S-phenylsulfonimidoyl]-3-isopropyl-2-[(2-methylprop-2-yl-sulfonyl)-prop-2-ynyl-amino]pent-4-enoic acid ethyl ester 
• 616234-13-0 (+)-(E,S_S,2S,3R)-5-[N-methyl-S-phenylsulfonimidoyl]-3-phenyl-2-[(2-methylprop-2-yl-sulfonyl)-prop-2-ynyl-amino]pent-4-enoic acid ethyl ester 
• 616234-12-9 (+)-(E,S_S,2S,3R)-5-[N-methyl-S-phenylsulfonimidoyl]-3-cyclohexyl-2-[(2-methylprop-2-yl-sulfonyl)-prop-2-ynyl-amino]pent-4-enoic acid ethyl ester 
• 4381-25-3 (S)-S-methyl-S-phenylsulfoximine 
• 918637-16-8 (3R,4S,Z)-3-isopropyl-1-[(S)-N-methyl-S-phenylsulfonimidoyl]octa-1,7-dien-4-ol 
• 918637-18-0 triethyl((3R,4S,Z)-3-isopropyl-1-[(S)-N-methyl-S-phenylsulfonimidoyl]octa-1,7-dien-4-yloxy)triethylsilane 
• 918637-32-8 triethyl((1S,2R,3E,6Z)-2-isopropyl-4-[(S)-N-methyl-S-phenylsulfonimidoyl]cyclonona-3,6-dienyloxy)silane 
• 918637-21-5 triethyl((5S,6R,7E)-6-isopropyl-8-[(S)-N-methyl-S-phenylsulfonimidoyl]undeca-1,7,10-trien-5-yloxy)triethylsilane 
• 172748-29-7 (+)-(E,S)-4-methyl-1-(N-methyl-S-phenylsulfonimidoyl)-pent-2-ene 
• 34948-25-9 n-butylcopper 

Downstream Products

• 15934-34-6 (+)-(S)-Phenyl-N-methylbenzolsulfonimidat 
• 30004-67-2 N,S-dimethyl-S-phenylsulfoximine 
• 67087-36-9 S-butyl-N-methyl-S-phenylsulfoximine 
• 69766-05-8 S-Allyl-N-methyl-S-phenylsulfoximin 
• 69766-06-9 S-Cyclopentyl-N-methyl-S-phenylsulfoximin 
• 69766-04-7 S-Benzyl-N-methyl-S-phenylsulfoximin 
• 33957-73-2 Benzenesulfinic acid (R)-methylamide 
• 111698-33-0 (R)-methyl benzenesulfinate 
• 112425-42-0 (S)-methyl benzenesulfinate 
• 17246-91-2 N¹,N¹,N²-Trimethyl-benzolsulfonamidin 

Relevant academic research and scientific papers

Cross-Coupling Reaction of Alkenyl Sulfoximines and Alkenyl Aminosulfoxonium Salts with Organozincs by Dual Nickel Catalysis and Lewis Acid Promotion

In this article, the cross-coupling reaction (CCR) of exocyclic, axially chiral, and acyclic alkenyl (N-methyl)sulfoximines with alkyl- and arylzincs is described. The CCR generally requires dual Ni catalysis and MgBr2 promotion, which is effective in diethyl ether but not in THF. NMR spectroscopy revealed a complexation of alkenyl sulfoximines by MgBr2 in diethyl ether, which suggests an acceleration of the oxidative addition through nucleofugal activation. The CCR of alkenyl sulfoximines generally proceeds in the presence of Ni(dppp)Cl2 as a precatalyst and MgBr2 with alkyl- and arylzincs with a high degree of stereoretention at the C and the S atom. CCR of axially chiral alkenyl sulfoximines with Ni(PPh3)2Cl2 as a precatalyst and ZnPh2 does not require salt promotion and is stereoretentive. The reaction with Zn(CH2SiMe3)2, however, demands salt promotion and is not stereoretentive. CCR of axially chiral α-methylated alkenyl sulfoximines afforded persubstituted axially chiral alkenes with high selectivity. Alkenyl (N-triflyl)sulfoximines engage in a stereoretentive CCR with Grignard reagents and Ni(PPh3)2Cl2. Ni-Catalyzed and MgBr2-promoted CCR of E-configured acyclic alkenyl sulfoximines and aminosulfoxonium salts with ZnPh2 and Zn(CH2SiMe3)2 is stereoretentive with Ni(dppp)Cl2 and Ni(PPh3)2Cl2. CCRs of acyclic alkenyl sulfoximines and alkenyl aminosulfoxonium salts, carrying a methyl group at the α position, take a different course and give alkenyl sulfinamides under stereoretention at the S and C atom. CCR of acyclic, exocyclic, and axially chiral alkenyl sulfoximines has been successfully applied to the stereoselective synthesis of homoallylic alcohols, exocyclic alkenes, and axially chiral alkenes, respectively.

Acid catalyzed alcoholysis of sulfinamides: Unusual stereochemistry, kinetics and a question of mechanism involving sulfurane intermediates and their pseudorotation

The synthesis of optically active sulfinic acid esters has been accomplished by the acid catalyzed alcoholysis of optically active sulfinamides. Sulfinates are formed in this reaction with a full or predominant inversion of configuration at chiral sulfur or with predominant retention of configuration. The steric course of the reaction depends mainly on the size of the dialkylamido group in the sulfinamides and of the alcohols used as nucleophilic reagents. It has been found that bulky reaction components preferentially form sulfinates with retention of configuration. It has been demonstrated that the stereochemical outcome of the reaction can be changed from inversion to retention and vice versa by adding inorganic salts to the acidic reaction medium. The unusual stereochemistry of this typical bimolecular nucleophilic substitution reaction, as confirmed by kinetic measurements, has been rationalized in terms of the addition-elimination mechanism, A-E, involving sulfuranes as intermediates which undergo pseudorotations.

Spiro- and bicycloannulation of sulfoximine-substituted 2-hydroxy-dihydropyrans: Enantioselective synthesis of spiroketals, spiroethers, and oxabicycles and structure of dihydropyran oxocarbenium ions

A modular enantioselective synthesis of spiroketals, spiroethers, and oxabicycles, each containing a dihydropyran subunit, is described. It is based on the 2,2-spiro- and 2,6-bicycloannulation of sulfoximine-substituted 2-hydroxy-dihydropyrans. Key steps of the spiroannulations are the ring-closing metathesis of the corresponding 2,2-oxadienyl and 2,6-dienyl dihydropyrans and Prins cyclization of 2-alkenyl 2-hydroxy-dihydropyrans. Ring-closing metathesis of the corresponding 2,6-dienyl dihydropyrans gave oxabicycles with oxabicyclo[4.3.1]decane skeletons. These routes were extended to the synthesis of spiroketals and spiroethers incorporating additional annulated six-membered rings. Diastereoselective Prins cyclization of mono- and bicyclic 2-alkenyl-2-hydroxy-dihydropyrans was highly selective and afforded chloro-substituted spirocycles. Substituted 2-hydroxy-dihydropyrans were obtained through cyclization of δ-hydroxy ketones, which were synthesized from enantiomerically pure sulfoximine-substituted homoallylic alcohols through lithiation and trapping of the α-lithioalkenylsulfoximines with unsaturated aldehydes, followed by allylic oxidation. Inter- and intramolecular glycosidations of the 2-hydroxy-dihydropyrans with O- and C-nucleophiles proceeded with high stereoselectivities and furnished 2,6-trans-configured glycosides. Dihydropyran oxocarbenium ions are most likely intermediates in the glycosidations. According to ab initio calculations, sulfoximine- and trimethyl-substituted dihydropyran oxocarbenium ions adopt a half-chair-like conformation. The energy difference between the oxocarbenium ion with pseudoaxial and the one with pseudoequatorial methyl groups is very small. A transition state model for their reactions with nucleophiles is proposed. It features a half-chair-like conformation, a pseudoequatorial C6 substituent, and an anti-addition of the nucleophile along an axial trajectory to C2 that produces an anti-periplanar lone pair at the O atom. A similar transition state model allows a general explanation for the trans stereoselectivity of the reactions between C6-substituted dihydropyran oxocarbenium ions and nucleophiles. Spiroannulation of 2-hydroxy-dihydropyrans through RCDEM of the corresponding 2,2-dienyl dihydropyrans and Prins cyclization of 2-alkenyl dihydropyrans gave sulfoximine-substituted unsaturated spiroketals and spiroethers. RCDEM of 2,6-dienyl dihydropyrans afforded oxabicycles. A transition state model for the 2,6-trans-stereoselective glycosidation of dihydropyran oxocarbenium ions is proposed. Copyright

Asymmetric synthesis of densely functionalized medium-ring carbocycles and lactones through modular assembly and ring-closing metathesis of sulfoximine-substituted trienes and dienynes

An asymmetric synthesis of densely functionalized 7-11-membered carbocycles and 9-11-membered lactones has been developed. Its key steps are a modular assembly of sulfoximine-substituted C- and O-tethered trienes and C-tethered dienynes and their Ru-catal

Ring-closing metathesis of sulfoximine-substituted N-tethered trienes: Modular asymmetric synthesis of medium-ring nitrogen heterocycles

A synthesis of sulfoximine-substituted medium-ring nitrogen heterocycles (MRNHs) having a high degree of substitution has been developed. Its key steps are the modular asymmetric synthesis of sulfoximine-substituted N-tethered trienes and their Ru-catalyz

Anionic cross-coupling reaction of α-metallated alkenyl sulfoximines and alkenyl sulfoximines with cuprates featuring a 1,2-metal-ate rearrangement of sulfoximine-substituted higher order alkenyl cuprates and an α-metallation of alkenyl sulfoximines by cuprates

(E)- and (Z)-configured αlithioalkenyl sulfoximines, which are available through lithiation of the corresponding alkenyl sulfoximines, undergo a anionic cross-coupling reaction (ACCR) with organocuprates with formation of the corresponding alkenyl cuprates and sulfinamide. The alkenyl cuprates can be trapped by electrophiles. The ACCR presumably proceeds via the formation of a higher-order sulfoximine-substituted alkenyl cuprate, which undergoes a 1,2-metalate rearrangement whereby the sulfoximine group acts as the nucleofuge. The parent (E)- and (Z)-configured alkenyl sulfoximines suffer upon treatment with an organocuprate a deprotonation at the α-position with formation of the corresponding α-cuprioalkenyl sulfoximines. These derivatives also enter into a similar ACCR with organocuprates. The ACCR of sulfoximines substituted homoallylic alcohols allows a stereoselective access to enantio- and diastereopure substituted homoallylic alcohols.

Ortho-Lithiation of S-tert-butyl-S-phenylsulfoximines. New route to enantiopure sulfinamides via a de-tert-butylation reaction

The sulfoximine group proved to be an excellent ortho-directing group in lithiation reactions. Several electrophiles were used to afford the corresponding ortho-functionalized aryl sulfoximines in good yields. The use of prochiral electrophiles lead to mo

Asymmetric synthesis of fused bicyclic α-amino acids having a hexahydro-cyclopenta[c]pyridine skeleton via intramolecular Pauson-Khand reaction of 1-sulfonimidoyl-substituted 5-azaoct-1-en-7-ynes

An asymmetric synthesis of fused bicyclic amino acids having a hexahydro-cyclopenta[c]pyridine skeleton and carrying besides an enone structural element a substituent at the β-position is described. The key steps of the synthesis are a highly selective al

Asymmetric synthesis of isocarbacyclin based on the olefination-isomerization-coupling process with chiral sulfoximines

An asymmetric synthesis of isocarbacyclin (2) was achieved from ketone 7 by the olefination-isomerization-coupling process with chiral sulfoximines. The vinylic sulfoximine 6 (≥98% de) was prepared from ketone 7 and lithiosulfoximine 8 by an asymmetric olefination via an addition-elimination process. Model experiments, aiming at a rationalization of the asymmetric induction in the elimination of β-hydroxysulfoximines, with ketone 12 and lithiosulfoximine ent-8 revealed formation of the silyl ether 15 as an intermediate which eliminated LiOSiMe3 upon reaction with nBuLi under formation of (S,Z)-alkene 17 (≥98% de). Reaction of the C,O-dilithiosulfoximine 19 with CISiMe3 led to elimination of LiOSiMe3 and also gave 17 (≥98% de). Methylation of 19, however, furnished the corresponding α-methyl-substituted β-hydroxysulfoximines, 20 and 21, in a ratio of 75:25. Isomerization of sulfoximine 6 gave the allylic sulfoximine 5 (96% de) whose absolute configuration was determined by X-ray structure analysis. Cross-coupling reaction of 5 with cuprate 23 delivered with high regioselectivity alkene 25. A similar reaction of 5 with the organocopper reagent 26, which was prepared from (benzyloxy)methylmagnesium chloride, in the presence of BF3 · OEt2 and halide afforded alkene 27. Ketone 28 is a potential starting material for the asymmetric synthesis of 3-oxaisocarbacyclin. Besides alkenes 25 and 27 sulfinamide 24 (97% ee), whose conversion to 8 has been already described, was isolated in 90% yield. The key step in the sequence leading to the construction of the ω-side chain was the deprotonation of ketone 4b with a complex of lithium (R.R)-bis(α-phenylethyl)amide and lithium chloride, 29 - LiCl, which gave enolate 3. The use of ent-29 - LiCl in the deprotonation of 4b afforded the isomeric enolate 30. Enolates 3 and 30 were trapped as the silyl ethers 31 (90% ie) and 32 (92% ie), respectively. The aldol reaction of 3 with (E)-octenal proceeded highly selective in regard to C-12 but unselective in regard to C-13 and gave aldols 34 (42%) and epi-34 (36%). It was at the stage of the aldol reaction of 3 where the unwanted diastereomers 35 and epi-35, stemming from 30, could be separated. Reduction of ketones 34 and epi-34 afforded diols 36 (≥98% de) and 37 (93% de), respectively. The Pd-catalyzed rearrangement of the allylic diacetates 39 and 41 was highly stereoselective (≥98% de) but incomplete and led to formation of mixtures of 40 and 39 as well as of 42 and 41 in ratios of 84:16 and 86:14, respectively. A two-step oxidation of alcohol 43, contaminated by 5% of the isomeric alcohol stemming from acetate 39, via aldehyde 44 gave after purification by crystallization isocarbacyclin (2) in 38% yield. Diol 45, having the undesired (15R) configuration, was selectively oxidized with dichlorodicyanobenzoquinone to enone 46 (81%).

Regio- and enantioselective substitution of acyclic allylic sulfoximines with butylcopper in the presence of lithium iodide and boron trifluoride

Enantiomerically pure N-methyl-, N-benzyl-, and N-(methoxyethyl)-S-(phenyl)cinnamylsulfoximmes as well as the corresponding crotylsulfoximines have been prepared from N-methyl-, N-benzyl-, and N-(methoxyethyl)-S-(lithiomethyl)sulfoximines and carbonyl com