85664-76-2

Upstream product

• 85664-75-1 2,2-Dimethyl-propionic acid 2-[(E)-tert-butylimino]-1-phenyl-ethyl ester 
• 373392-28-0 trimethylacetic acid 1-phenylallyl ester 
• 82937-45-9 N-(2-phenylethylidene)-1,1-dimethylethanamine N-oxide 
• 3282-30-2 pivaloyl chloride 
• 4393-06-0 1-Phenyl-2-propen-1-ol 

Downstream Products

• 373392-18-8 (1'R,2'S,5'R)-8'-phenylmenthyl (2Z,4R)-4-phenyl-4-pivaloyloxy-2-butenoate 
• 373392-36-0 (1'R,2'S,5'R)-8'-phenylmenthyl (2E,4S)-4-phenyl-4-pivaloyloxy-2-butenoate 
• 25779-13-9 (S)-1-phenyl-1,2-ethanediol 
• 16355-00-3 (R)-1-phenyl-1,2-ethanediol 
• 373392-29-1 2,2-Dimethyl-propionic acid (R)-2-hydroxy-1-phenyl-ethyl ester 
• 373392-41-7 2,2-Dimethyl-propionic acid (S)-2-hydroxy-1-phenyl-ethyl ester 

Relevant academic research and scientific papers

Enantioconvergent synthesis by sequential asymmetric Horner-Wadsworth-Emmons and palladium-catalyzed allylic substitution reactions

A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different α-oxygen-substituted, racemic aldehydes were initially transformed by asymmetric HWE reactions into mixtures of two major α,β-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution reactions with carbon, nitrogen, and oxygen nucleophiles. In this latter step, the respective (E) and (Z) alkene substrate isomers were observed to react with opposite stereospecificity: the (E) alkene reacted with retention and the (Z) alkene with inversion of stereochemistry with respect to both the allylic stereocenter and the alkene geometry. Thus, a single γ-substituted ester was obtained as the overall product, in high isomeric purity. The method was applied to a synthesis of a subunit of the iejimalides, a group of cytotoxic macrolides.

α-Oxygenation of Aldehydes and Cyclic Ketones by Acylation-Rearrangement of Nitrones

The reaction of N-tert-butylnitrones (1a-e) of aldehydes and N-methylnitrones (2 and 3) of cyclic ketones with acid chlorides in the presence of triethylamine afforded α-acyloxy imines by rearrangement of N-vinyl-O-acylhydroxylamine intermediates.Hydrolysis of the α-acyloxy imines gave α-acyloxy aldehydes and ketones.The acylation-rearrangement reaction offers a new method for α-oxygenation of carbonyl compounds.