128917-51-1

Upstream product

• 4124-41-8 p-toluenesulfonylanhydride 
• 141-97-9 ethyl acetoacetate 
• 98-59-9 p-toluenesulfonyl chloride 
• 4341-76-8 Ethyl 2-butynoate 
• 104-15-4 toluene-4-sulfonic acid 

Downstream Products

• 945-93-7 ethyl (Z)-3-phenylbut-2-enoate 
• 133572-04-0 ethyl (Z)-3-(2-methoxyphenyl)but-2-enoate 
• 133572-05-1 (E)-ethyl 3-(2-methoxyphenyl)but-2-enoate 
• 945-93-7 ethyl (E)-3-phenylbut-2-enoate 

Relevant academic research and scientific papers

Asymmetric synthesis of (S)-3-methyleneglutamic acid and its N-Fmoc derivative via Michael addition–elimination reaction of chiral glycine Ni (II) complex with enol tosylates

The use of chiral Ni (II)-complexes of glycine Schiff bases has recently emerged as a leading methodology for asymmetric synthesis of structurally diverse Tailor-Made Amino Acids, playing a key role in the design of modern pharmaceuticals. Here, we report first example of enantioselective preparation of (S)-3-methyleneglutamic acid and its N-Fmoc derivative via a new type of Michael addition–elimination reaction between chiral nucleophilic glycine equivalent and enol tosylates. This reaction was found to proceed with excellent yield (91%) and diastereoselectivity (>99/1 de) allowing straightforward asymmetric synthesis of (S)-3-methyleneglutamic acid derivatives and analogues. The observed results bode well for general application of this Ni (II) complex approach for preparation and biological studies of this previously unknown type of Tailor-Made Amino Acids.

Palladium-Catalyzed Regio- and Stereoselective Hydrosulfonation of Propiolate Esters

An efficient palladium-catalyzed addition reaction of alkyl- and arylsulfonic acids to propiolate esters to yield alkenyl sulfonates is demonstrated. The formation of alkenyl sulfonates is highly regio- and stereoselective with favorable yields of up to 95%, and two of the alkenyl sulfonates are utilized for a Sonogashira cross-coupling reaction to produce (Z)-1,3-enynoates.

Synthesis of 2-Arylpyridopyrimidinones, 6-Aryluracils, and Tri- and Tetrasubstituted Conjugated Alkenes via Pd-Catalyzed Enolic C-O Bond Activation-Arylation

A new and efficient approach for the synthesis of biologically important 2-aryl-4H-pyrido[1,2-a]pyrimidin-4-ones and 6-aryluracils via previously unknown Pd-catalyzed enolic C-OH activation-arylation of pyridopyrimidin-2,4-diones and barbituric acids, res

General, robust, and stereocomplementary preparation of β-ketoester enol tosylates as cross-coupling partners utilizing TsCl-N-methylimidazole agents

(Chemical Equation Presented) We have developed a general, robust, and cost-effective method for the (E)- or (Z)-stereocomplementary enol tosylation of β-ketoesters using TsCl-N-methylimidazole (NMI)-Et3N or LiOH. TsCl coupled with NMI formed a

Controlling olefin geometry with Pd catalysis: Selective formation of Z-olefins from both E-and Z-allylic carbonates

The palladium-catalyzed formation of Z-olefins from allylic carbonates and a variety of protected dialkyl aminomalonates is reported. The reaction is selective for the Z-isomer, and either acetyl, Boc, or formyl protecting groups are tolerated. The Z-olef

Fast and regioselective Heck couplings with N-acyl-N-vinylamine derivatives

Highly regioselective Heck couplings of aryl inflates with N-acyl-N-vinylamines lacking an N-alkyl substituent were achieved with reaction times of approximately 1 h in yields ranging from 62 to 98% using 1.5 mol % of Pd2(dba)3, 3 mol % of DPPF, and diethylisopropylamine in dioxane. The efficiency of these cross-couplings were studied with several N-vinylamides and an example each of an N-vinylcarbamate and an N-vinylurea. The Heck coupling products easily underwent acidic hydrolysis to the corresponding aryl methyl ketone or in situ hydrogenation in the presence of (Ph 3P)3RhCl under a hydrogen atmosphere to provide the N-acyl derivatives of pharmaceutically relevant benzylic amines. The coupling of a vinyl triflate and more interestingly a vinyl tosylate to N-vinyl acetamide was also studied affording a 2-acylamino-1,3-butadiene with the same high regioselectivity in preference for the α-isomer. This result suggests that Heck couplings of electron-rich alkenes with vinyl tosylates also follow a cationic pathway.

Synthesis of Enol Tosylates of β-Keto Esters

Some enol tosylates of β-keto esters were prepared by reacting the keto esters with p-tolylsulphonic anhydride in the presence of potassium tert-butoxide in THF and tert-butyl alcohol.