20288-54-4

Upstream product

• 1589-82-8 phenylmagnesium bromide 
• 159263-57-7 (R)-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-glucofuranos-3-yl tert-butanesulfinate 
• 7417-73-4 benzyl t-butyl sulfide 
• 67734-35-4 (R)-tert-butyl tert-butanethiosulfinate 
• 108-88-3 toluene 
• 100-39-0 benzyl bromide 

Relevant academic research and scientific papers

Stereoselective synthesis of isoindolinones and tert-butyl sulfoxides

A reaction of Grignard reagents with an optically pure N-sulfinylimine derived from methyl 2-formylbenzoate yields enantioenriched isoindolinones and tert-butyl sulfoxides. The products are formed by the addition of the nucleophile to N-sulfinylimine followed by cyclization to form N-tert-butylsulfinylisoindolinone, which readily undergoes substitution with a second equivalent of Grignard reagent. The reaction can be carried out in dichloromethane at room temperature or at elevated temperatures without any loss of stereoselectivity. The use of nucleophiles other than Grignard reagents has also been investigated.

DMAP-Catalysed Sulfinylation of Diacetone- D -Glucose: Improved Method for the Synthesis of Enantiopure tert-Butyl Sulfoxides and tert-Butanesulfinamides

An improved method for the tert-butanesulfinylation of diacetone glucose with tert-butanesulfinyl chloride is reported. The method is based on a beneficial effect of catalytic DMAP, which enhances both the rate of the reaction and the enantioselectivity of the process to give (R S)-diastereomer 2 R S with a 94 % de and in quantitative yield. (R S)-DAG sulfinate ester 2 R S is an excellent intermediate for the synthesis of enantiopure tert-butyl sulfoxides. Grignard agents and organolithium reagents can displace smoothly the diacetone glucose moiety to give synthetically relevant enantiopure sulfoxides, including highly functionalized derivatives, in high yields and with high enantioselectivities. (R S)-DAG sulfinate ester 2 R S is also an excellent N-sulfinylating agent; simple addition of LiHMDS (lithium hexamethyldisilazide) in THF gives (S S)-tert-butanesulfinamide, and N-tert-butanesulfinylimines are then formed in a two-step one-pot manner. N-Alkylated tert-butanesulfinamides are formed by the condensation of 2 R S with lithium amides.

Investigation of steric and electronic effects in the copper-catalysed asymmetric oxidation of sulfides

Steric and electronic effects in the copper-catalysed asymmetric oxidation of aryl benzyl, aryl alkyl and alkyl benzyl sulfides have been investigated. The presence of an aryl group directly attached to the sulfur is essential to afford sulfoxides with high enantioselectivities, with up to 97% ee for 2-naphthyl benzyl sulfoxide, the highest enantioselectivity achieved to date for copper-catalysed asymmetric sulfoxidation. In contrast, the benzyl substituent can be replaced by sterically comparable groups with no effect on enantioselectivity. Copper-mediated oxidation of substituted aryl benzyl sulfides display modest steric and electronic effects resulting in comparable or lower enantioselectivities to those obtained with the unsubstituted benzyl phenyl sulfide.

Enantioselective synthesis of benzyl tert-butyl sulfoxides

Enantiomerically pure benzyl sulfoxides are effective tools for the formation of new C-C bonds with control of configuration at new stereogenic centres. The reaction of enantioenriched tert-butyl tert-butanethiosulfinate with benzyllithium derivatives, ob