159951-07-2

Upstream product

• 50635-99-9 (+)-(S)-(N-methylphenylsulfonimidoyl)methyllithium 
• 103-79-7 1-phenyl-acetone 
• 159951-08-3 (-)-(S,Z)-N-methyl-S-(2-methyl-3-phenyl-2-propenyl)-S-phenylsulfoximine 
• 42764-56-7 (+/-)-S-lithiomethyl S-phenyl N-methyl sulfoximine 
• 573681-21-7 (+)-(3S,4R,5Z)-2,5-dimethyl-6-[(S)-N-methyl-S-phenylsulfonimidoyl]-4-phenyl-5-hexen-3-ol 
• 473434-00-3 (+)-(S)-S-[(1Z,3R,4S)-2,5-dimethyl-3-phenyl-4-(triethylsilyloxy)hex-1-enyl]-N-methyl-S-phenylsulfoximine 

Downstream Products

• 159951-08-3 (-)-(S,Z)-N-methyl-S-(2-methyl-3-phenyl-2-propenyl)-S-phenylsulfoximine 

Relevant academic research and scientific papers

Asymmetric synthesis of substituted homoallyl alcohols, halomethyl tetrahydrofurans, and chloro-amino sulfones from allyltitanium sulfoximines and α-hetero aldehydes

Asymmetric syntheses of the iodomethyl-substituted bicyclic tetrahydrofuran 22 and the chloro-amino sulfone 30 from the allylic sulfoximine 15 and the α-hetero aldehydes 2 and 23, respectively, are described. Further examples for the asymmetric synthesis

Asymmetric synthesis of protected β-substituted and β,β-disubstituted β-amino acids bearing branched hydroxyalkyl side chains and of protected 1,3-amino alcohols with three contiguous stereogenic centers from allylic sulfoximines and aldehydes

We describe a new method for the asymmetric synthesis, from allylic sulfoximines and aldehydes, of N,O-protected, cyclic and acyclic, β-substituted and β,β-disubstituted δ-hydroxy-β-amino acids and of N,O-protected 1,3-amino alcohols, both possessing three contiguous stereogenic centers. Treatment of enantiomerically pure, acyclic allylic sulfoximines with aldehydes after successive lithiation and titanation afforded sulfonimidoyl-substituted homoallylic alcohols with high regio- and diastereoselectivities. Diastereomerically pure, cyclic, sulfonimidoyl-substituted homoallylic alcohols were synthesized in a similar manner from the corresponding enantiomerically pure, cyclic allylic sulfoximines and isobutyraldehyde. A highly diastereoselective amination of the sulfonimidoyl-substituted homoallylic alcohols with the generation of secondary and tertiary C atoms and formation of the sulfonimidoyl-substituted, protected 1,3-amino alcohols (oxazinones) was achieved by the carbamate method, through cyclization of the corresponding carbamates after their lithiation with nBuLi. The sulfonimidoyl-substituted, monocyclic and bicyclic oxazinones were converted into protected, acyclic and cyclic, β-substituted and β,β-disubstituted β-amino acids and protected 1,3-amino alcohols by two different routes: the carbanion route and the substitution route. The carbanion route involves: (1) a double lithiation of the protected β-amino sulfoximines, (2) treatment of the dilithiated sulfoximines with electrophiles, and (3) reductive removal of the sulfonimidoyl group. By the carbanion route, double lithiation of the sulfonimidoyl-substituted oxazinones with nBuLi gave the corresponding dilithium salts, which reacted readily with a number of electrophiles to give the corresponding α-substituted sulfoximines in good yields. Reduction of the sulfoximines with Raney nickel afforded the corresponding protected monocyclic and bicyclic 1,3-amino alcohols and the protected acyclic and cyclic β-amino acids in good yields. The substitution route involves: (1) a facile substitution of the sulfonimidoyl group by a Cl atom, and (2) a substitution of the Cl atom of the protected β-amino chlorides by a cyano group. Treatment of the sulfoximines with ClCO2Me readily afforded the corresponding β-amino chlorides in good yields, and so treatment of alkyl sulfoximines with chloroformates seems to be a general method for the replacement of an N-methylsulfonimidoyl group by a Cl atom. Introduction of a cyano group was achieved through treatment of chlorides with NaCN, which gave the corresponding β-amino nitriles in good yields. Finally, hydrolysis of the nitriles afforded the protected acyclic and cyclic, β-substituted and β,β-disubstituted β-amino acids. Treatment of the protected β-amino sulfoximines with ClCO2Me gave - besides the corresponding chlorides - methyl (S)-N-phenyl-sulfinylcarbamate with ≥ 99% ee in good yield. Treatment of the sulfinamide with MeMgCl afforded (S)-methyl phenyl sulfoxide with 97% ee, and this could be converted with complete retention of configuration into (S)-N,S-dimethyl-S-phenylsulfoximine, the starting material for the synthesis of the allylic sulfoximines used in this work. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

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

Asymmetric synthesis of disubstituted C-silylated homoallylic alcohols from lithiated allylic and vinylic sulfoximines

Lithiation, titanation and hydroxyalkylation of allylic N-methyl sulfoximines 1-4 gave with ≥95% de the anti-Z-configurated homoallylic alcohols 5-9. Lithiation of 6b and 8b with MeLi readily produced the lithiated vinylic sulfoximines (Z)-12 and (Z)-13, respectively. Ni-catalyzed substitution of (Z)-12 and (Z)-13 with PhLi and 1,5-silyl migration yielded with ≥98% de the disubstituted C-silylated homoallylic alcohols (Z)-14 and (Z)-15, respectively. (Z)-15 thus obtained from (Z)-13 had an ee-value of ≥98%.

Rearrangement of allylic sulfoximines to allylic sulfinamides

Thermolysis of the enantiomerically pure allylic sulfoximines 3a, b leads to their partial rearrangement to the isomeric allylic sulfinamides 5a, b and 6a, b, respectively, with complete retention of configuration at the S-atom. Racemization of the allyli