212378-97-7

Basic information

• Product Name: (R(S))-N-(1-phenylethylidene)-tert-butanesulfinamide
• Synonyms: (R(S))-N-(1-phenylethylidene)-tert-butanesulfinamide
• CAS NO: 212378-97-7
• Molecular Weight: 223.339
• Mol File: 212378-97-7.mol

Chemical Properties

• CAS DataBase Reference: (R(S))-N-(1-phenylethylidene)-tert-butanesulfinamide(CAS DataBase Reference)
• NIST Chemistry Reference: (R(S))-N-(1-phenylethylidene)-tert-butanesulfinamide(212378-97-7)
• EPA Substance Registry System: (R(S))-N-(1-phenylethylidene)-tert-butanesulfinamide(212378-97-7)

Safety Data

• Hazardous Substances Data: 212378-97-7(Hazardous Substances Data)

Upstream product

• 350-03-8 methyl-3-pyridylketone 
• 196929-78-9 (R)-2-methylpropane-2-sulfinamide 
• 146374-27-8 S-tert-butylsulfinimide 
• 98-86-2 acetophenone 
• 1826-67-1 vinyl magnesium bromide 
• 1172578-24-3 C₁₂H₁₆ClNOS 

Downstream Products

• 1426585-76-3 pinacol (R)-1-N-sulfinylphenylmethyl-1-boronate 
• 1426585-77-4 pinacol (R)-1-N-sulfinylphenylmethyl-1-boronate 
• 131154-18-2 (R)-(1-methyl-1-phenyl-but-3-enyl)amine 
• 131154-23-9 N-((R)-1-Methyl-1-phenyl-but-3-enyl)-acetamide 
• 1585970-62-2 C₁₉H₂₆N₂O₃S 
• 1373154-77-8 (R)-4,4,4-trifluoro-3-hydroxy-1,3-diphenylbutan-1-one 
• 20826-48-6 (R)-N-(1-phenylethyl)benzamide 
• 1354630-29-7 (Rs,1S,3R)-N-((E)-3-hydroxy-1,5-diphenyl-3-(trifluoromethyl)pent-4-enyl)tert-butanesulfinamide 

Relevant articles and documents

Direct synthesis of chiral aziridines from N-tert-butyl-sulfinylketimines

The direct preparation of a range of variously substituted chiral tert-butylsulfinylketimines was achieved in good yield (41-90%), with relatively rapid reaction times (4-15 hours); their synthetic application was examined through the reaction with the yl

Structure- and Ligand-Based Discovery of Chromane Arylsulfonamide Nav1.7 Inhibitors for the Treatment of Chronic Pain

Using structure- and ligand-based design principles, a novel series of piperidyl chromane arylsulfonamide Nav1.7 inhibitors was discovered. Early optimization focused on improvement of potency through refinement of the low energy ligand conformation and mitigation of high in vivo clearance. An in vitro hepatotoxicity hazard was identified and resolved through optimization of lipophilicity and lipophilic ligand efficiency to arrive at GNE-616 (24), a highly potent, metabolically stable, subtype selective inhibitor of Nav1.7. Compound 24 showed a robust PK/PD response in a Nav1.7-dependent mouse model, and site-directed mutagenesis was used to identify residues critical for the isoform selectivity profile of 24.

Racemization free protocol for the synthesis of N - Tert -butanesulfinyl ketimines

Figure presented. A general and robust racemization-free protocol for the synthesis of a variety of N-tert-butanesulfinyl ketimines is reported. Reaction progress was monitored by 1H NMR using the nonperturbing internal standard diglyme, and ke

Studies towards the total asymmetric synthesis of the pentacyclic indole alkaloid arboflorine: Asymmetric synthesis of a key intermediate

The synthesis of a plausible key intermediate for a biomimetic asymmetric synthesis of indole alkaloid arboflorine is described. The method featured the use of Ellman's sulfinamide chemistry for the establishment of the first chiral center, and the Polonovski-Potier reaction for the formation of the -aminonitrile moiety. Georg Thieme Verlag Stuttgart New York.

Transition-Metal-Free Hydrogen Autotransfer: Diastereoselective N-Alkylation of Amines with Racemic Alcohols

A practical method for the synthesis of α-chiral amines by alkylation of amines with alcohols in the absence of any transition-metal catalysts has been developed. Under the co-catalysis of a ketone and NaOH, racemic secondary alcohols reacted with Ellman's chiral tert-butanesulfinamide by a hydrogen autotransfer process to afford chiral amines with high diastereoselectivities (up to >99:1). Broad substrate scope and up to a 10 gram scale production of chiral amines were demonstrated. The method was applied to the synthesis of chiral deuterium-labelled amines with high deuterium incorporation and optical purity, including examples of chiral deuterated drugs. The configuration of amine products is found to be determined solely by the configuration of the chiral tert-butanesulfinamide regardless of that of alcohols, and this is corroborated by DFT calculations. Further mechanistic studies showed that the reaction is initiated by the ketone catalyst and involves a transition state similar to that proposed for the Meerwein–Ponndorf–Verley (MPV) reduction, and importantly, it is the interaction of the sodium cation of the base with both the nitrogen and oxygen atoms of the sulfinamide moiety that makes feasible, and determines the diastereoselectivity of, the reaction.

Microwave-Enhanced Asymmetric Transfer Hydrogenation of N-(tert-Butylsulfinyl)imines

Microwave irradiation has considerably enhanced the efficiency of the asymmetric transfer hydrogenation of N-(tert-butylsulfinyl)imines in isopropyl alcohol catalyzed by a ruthenium complex bearing the achiral ligand 2-amino-2-methylpropan-1-ol. In addition to shortening reaction times for the transfer hydrogenation processes to only 30 min, the amounts of ruthenium catalyst and isopropyl alcohol can be considerably reduced in comparison with our previous procedure assisted by conventional heating, which diminishes the environmental impact of this new protocol. This methodology can be applied to aromatic, heteroaromatic and aliphatic N-(tert-butylsulfinyl)ketimines, leading, after desulfinylation, to the expected primary amines in excellent yields and with enantiomeric excesses of up to 96 %. Microwave irradiation promotes the asymmetric transfer hydrogenation of N-(tert-butylsulfinyl)imines in 2-propanol catalysed by a ruthenium complex bearing an achiral β-amino alcohol as ligand. After desulfinylation, α-branched primary amines containing aromatic, heteroaromatic and aliphatic substituents are obtained in excellent yields and with enantiomeric excesses of up to 96 %.

Microwave-assisted solvent-free synthesis of enantiomerically pure N-(tert-butylsulfinyl)imines

A simple, environmentally friendly, and very efficient procedure for the synthesis of optically pure N-(tert-butylsulfinyl)imines has been developed with microwave-promoted condensation of aldehydes and ketones using (R)-2-methylpropane-2-sulfinamide in the presence of Ti(OEt)4, under solvent-free conditions. This procedure allows for the preparation of a variety of sulfinyl aldimines with excellent yields and purities in only 10 min, making any further purification of the imines unnecessary. Several sulfinyl ketimines have also been prepared in good yields by extension of the reaction times to 1 h. This methodology has proved to be equally efficient for the synthesis of aromatic, heteroaromatic, and aliphatic N-(tert-butylsulfinyl)imines. Conventional heating has also been shown to be useful to promote these reactions, especially for the synthesis of aldimines.

A versatile Ru catalyst for the asymmetric transfer hydrogenation of both aromatic and aliphatic sulfinylimines

A highly efficient Ru catalyst based on an achiral, very simple, and inexpensive amino alcohol ligand (2-amino-2-methylpropan-1-ol) has been developed for the asymmetric transfer hydrogenation (ATH) of chiral N-(tert-butylsulfinyl)imines. This complex is able to catalyze the ATH of both aromatic and the most challenging aliphatic sulfinylimines by using isopropyl alcohol as the hydrogen source. The diastereoselective reduction of aromatic, heteroaromatic, and aliphatic sulfinylketimines, including sterically congested cases, over short reaction times (1-4 h), followed by desulfinylation of the nitrogen atom, affords the corresponding highly enantiomerically enriched (ee up to >99%) α-branched primary amines in excellent yields. The same ligand was equally effective for the synthesis of both (R)- and (S)-amines by using the appropriate absolute configuration in the iminic substrate. DFT mechanistic studies show that the hydrogen-transfer process is stepwise. Moreover, the origin of the diastereoselectivity has been rationalized.

Synthesis of 3-aryl-3-pyrrolines and 3-arylpyrroles via spontaneous rearrangement of N-sulfinyl 2-aryl-2-vinylaziridines

Addition of vinylmagnesium bromide across chiral -chloro N-tert-butanesulfinyl ketimines afforded 3-aryl-1-(tert-butanesulfinyl)-3- pyrrolines in high yield (65-91%) after purification by means of recrystallization from diethyl ether. The synthesis of the

Asymmetric synthesis of new chiral N-sulfinyl 2,2-disubstituted aziridines by Grignard additions across α-chloro N-sulfinyl ketimines

Reaction of chiral α-chloro N-tert-butanesulfinyl ketimines with Grignard reagents afforded new chiral N-sulfinyl 2,2-disubstituted aziridines in good to excellent diastereomeric ratio (dr up to 98:2). The 1,2,2-trisubstituted aziridines were isolated in