78935-61-2

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 101-97-3 Ethyl 2-phenylethanoate 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 78279-92-2 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclo-hexadiene 
• 2882-19-1 ethyl 2-phenyl-2-bromoacetate 

Downstream Products

• 130473-96-0 Ethyl 3-morpholino-2-phenylpropionate 
• 13622-58-7 ethyl 2-phenyl-3-(pyrrolidin-1-yl)propanoate 
• 90784-42-2 ethyl 3,3,3-trifluoro-2-phenylpropionate 
• 130474-03-2 N-p-tolyl-3-phenylazetidin-2-one 
• 14815-74-8 ethyl 2-phenylpent-4-enoate 
• 130473-95-9 2-Phenyl-3-p-tolylamino-propionic acid ethyl ester 
• 643-77-6 fluoro-phenyl-acetic acid ethyl ester 
• 300679-54-3 3-Morpholin-4-yl-2,3-diphenyl-propionic acid ethyl ester 
• 300679-55-4 4-Methyl-2-phenyl-3-piperidin-1-yl-pentanoic acid ethyl ester 
• 130473-94-8 2-Phenyl-3-phenylamino-propionic acid ethyl ester 

Relevant academic research and scientific papers

Organosilicon Reducing Reagents for Stereoselective Formations of Silyl Enol Ethers from α-Halo Carbonyl Compounds

Salt-free stereoselective synthesis of silyl enol ethers was achieved by treating α-halo carbonyl compounds with 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine. In this reaction, easily removable trimethylsilyl halides and 2,3,5,6-tetramethylpyrazine were generated as the reaction byproducts. Due to the inertness of the reaction byproducts, we found a one-pot transformation of the in situ generated silyl enol ethers into various α-functionalized carbonyls by reaction with Togni-II reagent or aldehydes.

Synthetic strategies for the synthesis and transformation of substituted pyrrolinones as advanced intermediates for rhazinilam analogues

The biaryl core structure of rhazinilam with its fixed dihedral angle is a pivotal element for its unique in vitro cytotoxic activity. Most of the related natural products are oxidized versions of rhazinilam. Replacing the sensitive pyrrole ring by a pyrrolinone ring is the basis of our initial strategy towards rhazinilam analogues. With this goal, variants of the sequence crossed Mukaiyama aldol reaction followed by the Staudinger reaction were studied. Reacting a suitably substituted acetophenone with O-methyl O-trimethylsilyl ketene acetal gave pyrrolinones 8a and 8b in good to excellent yields. These intermediates could be transformed in four high-yielding steps into the pyrrolic precursors 7a-c containing all the atoms necessary for the construction of rings A, B, and C of rhazinilam. Our studies illustrate a lack of stability of these intermediates. Alternative synthetic approaches towards this central biaryl core structure are described.

Preparation of β-aminoesters from ketene silyl acetals and N-(alkylamino)benzotriazoles

A wide variety of β-aminoesters are prepared in good yields by the reaction of lithium ester enolates derived from ketene silyl acetals with N-(alkylamino)benzotriazoles. The secondary β-aminoesters readily cyclize to β-lactams (2-azetidinones) on deprotonation.

Reactions of Trialkylsilyl Trifluoromethanesulfonates, II. - Synthesis of O-Alkyl-O-(trialkylsilyl)ketene Acetals and 2-(Trialkylsilyl)carboxylates

Alkyl carboxylates 2 are silylated by trialkylsilyl triflates 1 in the presence of triethylamine (3) to yield ketene acetals 4.In reactions of the esters 6 mixtures of ketene acetals 7 and at the α-carbon silylated esters 8 are obtained.Ethanoic acid esters and lactones are doubly silylated to give the products 11, 12, and 15, respectively.Under suitable conditions silylation of the esters 10 gives rise to the 2-trimethylsilylethanoic acid esters 13.The thermodynamically more stable products are obtained.Product distributions depend on the structure of the esters and the silylating agents 1.