1277102-71-2

Upstream product

• 100-39-0 benzyl bromide 
• 37472-52-9 α-methylmalonate mono-tert-butyl ester 
• 1277102-61-0 (S)-α-benzyl-α-methylmalonic acid diphenylmethyl ester tert-butyl ester 
• 1277102-59-6 benzyl(methyl)malonic acid cyclohexylmethyl tert-butyl ester 
• 1277102-46-1 methylmalonic acid diphenylmethyl tert-butyl ester 

Downstream Products

• 1277102-51-8 C₁₅H₂₁NO₃ 
• 1277102-61-0 (S)-α-benzyl-α-methylmalonic acid diphenylmethyl ester tert-butyl ester 

Relevant academic research and scientific papers

Enantioselective α-Alkylation of Benzylideneamino tert-Butyl Malonates by Phase-Transfer Catalysis

A new enantioselective synthetic method for the synthesis of α,α-dialkylmalonates with a quaternary carbon center was developed via α-alkylation of prochiral malonates by phase-transfer catalysis (PTC). Asymmetric α-alkylation of benzylideneamino tert-butyl α-methylmalonates under phase-transfer catalytic conditions in the presence of (S,S)-3,4,5-trifluorophenyl-NAS bromide afforded the corresponding α,α-dialkylmalonates in high yields (up to 97%) with excellent enantioselectivities (up to 98% ee). The products were then selectively hydrolyzed to chiral malonic monoacids under basic, acidic, or catalytic hydrogenation conditions.

Highly enantioselective synthesis of α,α-dialkylmalonates by phase-transfer catalytic desymmetrization

A novel enantioselective synthetic method for the construction of a quaternary carbon center from malonates via phase-transfer catalytic (PTC) alkylation has been developed. The asymmetric α-alkylation of diphenylmethyl tert-butyl α-alkylmalonates with alkylating agents under phase-transfer catalysis conditions (aq 50% KOH, toluene, 0°C) in the presence of (S,S)-3,4,5-trifluorophenyl-NAS bromide (8) as PTC catalyst afforded the corresponding α,α-dialkylmalonates in high chemical (up to 99%) and optical yields (up to 97% ee) which could be readily converted to versatile chiral intermediates. Notably, the direct double α-alkylations of diphenylmethyl tert-butyl malonate also provided the corresponding α,α-dialkylmalonates without loss of enantioselectivity. The synthetic potential of this method has been demonstrated by the preparation of α,α-dialkylamino acid and oxindole systems.