164931-77-5

Upstream product

• 930-68-7 cyclohexenone 
• 108-59-8 malonic acid dimethyl ester 
• 108-94-1 cyclohexanone 
• 67-56-1 methanol 
• 164931-75-3 (R)-3-[bis(benzyloxycarbonyl)methyl]cyclohexanone 

Downstream Products

• 177770-85-3 (R)-3-methoxycarbonylmethylcyclohexanone 
• 681280-68-2 (2S,3S)-2-allyl-3-[2-(tert-butyldiphenylsilanyloxy)-ethyl]-6-(phenyl-hydrazono)-cyclohexanone 
• 681280-65-9 (S)-3-[2-(tert-butyldiphenylsilanyloxy)-ethyl]-cyclohexanone 
• 681280-64-8 (S)-3-(2-hydroxy-ethyl)-cyclohexanone 

Relevant academic research and scientific papers

A practical large-scale synthesis of enantiomerically pure 3-[bis(methoxycarbonyl)methyl]cyclohexanone via catalytic asymmetric Michael reaction

A highly practical and efficient procedure for the large-scale (up to 6 mol) synthesis of enantiomerically pure (R)-3-[bis(methoxycarbonyl)methyl]cyclohexanone using an (R)-AlLibis(binaphthoxide) complex ((R)-ALB)-catalyzed asymmetric Michael reaction was developed. The reaction was successfully accelerated under highly concentrated conditions without lowering chemical yield or the high enantiomeric excess. Under these conditions, only 0.05 mol% of the catalyst forced the reaction to completion in 48 h. The work-up procedure was also improved and the enantiomerically pure compound was obtained as a white crystal in up to 95% yield without chromatographic separation. Finally, pre-manufacturing scale synthesis was performed. Using 0.1 mol% of the catalyst with 0.09 mol% of KO-t-Bu and MS 4 ?, the Michael reaction of 2-cyclohexenone (6.0 mol, 581 mL) with dimethyl malonate (6.0 mol, 686 mL) was completed in 24 h at ambient temperature to afford more than a kilogram of the enantiomerically pure product in 91% yield after three successive crystallizations. The described method renders the enantiomerically pure Michael adduct readily available on greater than kilo scale.

Enantioselective Synthesis and in Vivo Evaluation of Regioisomeric Analogues of the Antimalarial Arterolane

We describe the first systematic study of antimalarial 1,2,4-trioxolanes bearing a substitution pattern regioisomeric to that of arterolane. Conformational analysis suggested that trans-3″-substituted trioxolanes would exhibit Fe(II) reactivity and antipa

Synthesis of optically active (1R,4S,6S)-6-hydroxybicyclo[2.2.2]octan-2-one

Bicyclo[2.2.2]octanone is an important building block for the synthesis of bioactive compounds and natural products. Herein, we present a new synthetic route for the formation of (1R,4S,6S)-6-hydroxybicyclo[2.2.2]octan-2-one derivatives via a catalytic as

Catalytic Asymmetric β-C-H Functionalizations of Ketones via Enamine Oxidation

A chiral primary amine catalyzed oxidative β-C-H functionalization of ketone is described. The reaction proceeds via ketone enamine oxidation by IBX and enables highly enantioselective remote C-H functionalization of both cyclic and acyclic ketones, gener

Enzyme-Promoted Direct Asymmetric Michael Reaction by Using Protease from Streptomyces griseus

The direct asymmetric Michael addition of malonates and enones was promoted by protease from Streptomyces griseus for the first time. Yields of up to 84% with enantioselectivities of up to 98% enantiomeric excess (ee) were achieved under optimized conditi

Air- and water-tolerant rare earth guanidinium BINOLate complexes as practical precatalysts in multifunctional asymmetric catalysis

Shibasaki's REMB catalysts (REMB; RE = Sc, Y, La-Lu; M = Li, Na, K; B = 1,1′-bi-2-naphtholate; RE/M/B = 1/3/3) are among the most enantioselective asymmetric catalysts across a broad range of mechanistically diverse reactions. However, their widespread us

PRECATALYST FOR SHIBASAKI'S RARE EARTH METAL BINOLATE CATALYSTS

Disclosed herein are schemes for the synthesis of novel hydrogen-bonded rare earth- BINOLate precatalyst complexes, the precatalysts, per se, and their application for the generation of anhydrous REMB catalysts by cation-exchange from metal halides.

Mechanistic study of asymmetric Michael addition of malonates to enones catalyzed by a primary amino acid lithium salt

A mechanistic study was carried out for the asymmetric Michael addition reaction of malonates to enones catalyzed by a primary amino acid lithium salt to elucidate the origin of the asymmetric induction. A primary β-amino acid salt catalyst, O-TBDPS β-hom

An efficient organocatalytic method for highly enantioselective michael addition of malonates to enones catalyzed by readily accessible primary amine-thiourea

A practical and highly enantioselective Michael addition of malonates to enones catalyzed by simple and readily available bifunctional primary amine-thiourea derived from 1,2-diaminocyclohexane is reported. The addition of weak acids and elevated temperature (ca. 50 °C) improved the efficiency of the Michael reaction. This approach enables the efficient synthesis of 1,5-ketoesters with good yields, excellent enantioselectivities (up to 99% ee), and low loading (0.5-5 mol %) of simple chiral primary amine-thiourea catalysts, and is applicable in multigram scale synthesis.

Asymmetric michael addition of malonates to enones catalyzed by a primary Β-amino acid and its lithium salt

Highly enantioselective Michael addition of malonates to enones was achieved using a mixed catalyst consisting of a primary Β-amino acid, O-TBDPS (S)-Β-homoserine, and its lithium salt. Various cyclic and acyclic enones were converted into 1,5-ketoesters in high yields (up to 92%) with high enantioselectivity (up to 97% ee) under mild reaction conditions. Details of synthesis of the catalyst, optimization of the reaction conditions for the Michael addition reaction, and a plausible reaction mechanism are described.