300592-80-7

Upstream product

• 113543-35-4 (4S)-3-((2S)-2-bromo-3-methylbutanoyl)-4-benzyl-1,3-oxazolidin-2-one 
• 300592-68-1 3-[(2R)-3-methyl-2-phenylmethylthiobutanoyl]-(4S)-4-benzyl-1,3-oxazolidin-2-one 
• 100-53-8 phenylmethanethiol 

Downstream Products

• 1197375-36-2 (R)-(1-bromo-3-methylbutan-2-yl)(benzyl)sulfane 
• 1197375-39-5 (R)-1-[2-(benzylthio)-3-methylbutyl]-1H-imidazole 
• 300593-00-4 (2R,3R)-3-phenylmethylthio-4-methylpentan-2-ol 
• 300592-90-9 (2S,3R)-3-phenylmethylthio-4-methylpentan-2-ol 

Relevant academic research and scientific papers

Synthesis, structure and reactivity of some chiral benzylthio alcohols, 1,3-oxathiolanes and their S-oxides

A series of amino acid-derived chiral benzylthio alcohols have been prepared and characterized. A chiral mercapto alcohol derived from S-leucine has been used to form three chiral 2,4-disubstituted 1,3-oxathiolanes. One of these has been oxidized to the S-oxide and another to the S,S-dioxide. The cis and trans isomers have been characterized by 1H NMR in each case and it appears that thermal epimerisation at C-2 is possible at the sulfoxide oxidation state. The X-ray structure of major trans diastereomer of 2-phenyl-4-isobutyl-1,3-oxathiolane S,S-dioxide shows an envelope conformation with oxygen at the flap and an internal angle at sulfur of just 93.8°. This compound fragments upon flash vacuum pyrolysis at 700°C to give SO2, benzaldehyde and 4-methylpent-1-ene.

Application of chiral mixed phosphorus/sulfur ligands to palladium-catalyzed allylic substitutions

A modular approach to the synthesis of a class of mixed phosphorus/sulfur ligands was designed to identify important ligand structural features for enantioselective palladium-catalyzed allylic subsitutions of acyclic and cyclic ayllic esters. After a systematic variation of the ligand substituents at sulfur, phosphorus, and the ligand backbone, ligand 11k was found to be optimal in the palladium-catalyzed allylic substitution of 1,3-diphenylpropenyl acetate with dimethyl malonate or benzylamine in high yield and excellent enantioselectivity (95-98% ee). A similar optimization of the mixed phosphorus/sulfur ligand for the palladium-catalyzed allylic substitution of cycloalkenyl acetates showed that 49g afforded the highest enantioselectivities (91-97% ee). Application of this methodology to heterocyclic substrates was developed as an efficient approach to the enantioselective synthesis of 3-substituted piperidines and dihydrothiopyrans. Models for asymmetric induction are discussed based on the absolute stereochemistry of the products, X-ray crystallographic data, and NMR spectroscopic data for relevant π-allyl complexes.