166114-67-6

Upstream product

• 104-55-2 3-phenyl-propenal 
• 98-86-2 acetophenone 
• 13735-81-4 1-styrenyloxytrimethylsilane 
• 14371-10-9 (E)-3-phenylpropenal 
• 57957-24-1 N-(1-phenylvinyl)acetamide 

Downstream Products

• 174814-83-6 (S)-5-oxo-3,5-diphenylpentanoic acid 

Relevant academic research and scientific papers

Enantioselective organocatalytic Mukaiyama-Michael addition of silyl enol ethers to α,β-unsaturated aldehydes

(Chemical Equation Presented) A highly enantioselective, organocatalytic Mukaiyama-Michael addition reaction of silyl ethers and α,β- unsaturated aldehydes has been developed. The process, catalyzed by MacMillan's chiral imidazolidinone, affords δ-keto aldehydes in high yields (56-87%) and high enantioselectivities (85-97% ee). Moreover, the reaction is applicable to a wide range of silyl ethers and α,β-unsaturated aldehydes and, as such, provides access to a range of important synthetic building blocks.

Nucleophilicity parameters of enamides and their implications for organocatalytic transformations

The kinetics of the reactions of eleven substituted enamides with benzhydrylium ions (diarylcarbenium ions) were determined in acetonitrile solution. The second-order rate constants follow the correlation log k 2(20°C)=sN(E+N), which allowed us to derive reactivity parameters N and sN. With 4.6N parameters with the previously reported E parameters of typical Michael acceptors, α,β-unsaturated iminium ions, and the chlorinating agent hexachlorocyclohexa-2,4-dienone allowed us to reliably reproduce the experimental rate constants of the reactions with these electrophiles. The reactions of enamides with α,β-unsaturated iminium ions only proceeded in the presence of bases (e.g., 2,6-lutidine), which was explained by the low Lewis acidities of the iminium ions. The consequences of these results for the use of enamides in organocatalytic reactions are discussed. Nucleophile-specific parameters N and sN of enamides allowed a prediction of the rates of their reactions with various electrophiles and enabled a resolution of the mechanism of iminium-activated reactions of α,β-unsaturated aldehydes with enamides (see scheme).

Asymmetric direct michael addition of acetophenone to α,β- unsaturated aldehydes

The asymmetric direct Michael addition of ,-unsaturated aldehydes with acetophenone catalyzed by a Jorgensen-Hayashi-catalyst in methanol was developed and the corresponding Michael products of -keto aldehydes could be afforded in up to 82% yield and 98% ee. Georg Thieme Verlag Stuttgart.

Diphenylprolinol silyl ether as a catalyst in an enantioselective, catalytic, formal aza [3+3] cycloaddition reaction for the formation of enantioenriched piperidines

(Chemical Presented) Aza-ene reaction: Diphenylprolinol silyl ether was found to be an effective organocatalyst for the formal aza [3+3] cycloaddition reaction of a,b-unsaturated aldehydes and enecarbamates (see scheme). The reaction proceeds through an asymmetric catalytic ene reaction, isomerization, hydrolysis, and cyclization to afford piperidine derivatives in good yields and excellent enantioselectivities.

ORGANOCATALYSTS AND METHODS OF USE IN CHEMICAL SYNTHESIS

The present invention pertains generally to compositions comprising organocatalysts that facilitate stereo-selective reactions and the method of their synthesis and use. Particularly, the invention relates to metal-free organocatalysts for facilitation of stereo--selective reactions, and the method of their synthesis and use. These compounds have the structure of the Formulas (I) and (II). Where X is independently selected from CH2, N-Ra, O, S or C=O; Y is CH2, N-Ra, O, S or C=O, with the proviso that at least one of X or Y is CH2, and preferably both of X and Y are CH2; Ra is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6alkyl including a C3-C6 cyclic alkyl group, or an optionally substituted aryl group, preferably an optionally substituted phenyl group; Rb is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 acyclic or a a C3-C6 cyclic alkyl group, CHO, N(Me)O, CO(S)Ra or the group of Formula (III). Where Rc and Rd are each independently H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C12 alkyl, more preferably a C1-C6 alkyl, and an optionally substituted aryl group, or together Rc and Rd form an optionally substituted carbocyclic or optionally substituted heterocyclic ring; R1 is OH, OR, NR'R", NHC(=O)R, NHSO2R; R2 is H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C6 alkyl, an optionally substituted aryl group or a =O group (which establishes a carbonyl group with the carbon to which =O is attached; R3 is H, OH, F, C1, Br, I, Cl, an optionally substituted C1-C20 alkyl, alkenyl or alkynyl ("hydrocarbyl") group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl, such that the carbon to which R3 is attached has an R or S configuration; R is H, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group, R' and R" are each independently H, an optionally substituted C1-C20 alkyl group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group; or together R' and R" form an optionally substituted heterocyclic, preferably a 4 to 7 membered optionally substituted heterocyclic group or an optionally substituted heteroaryl ring with the nitrogen to which R' and R" are attached; and wherein said compound is free from a metal catalyst.