170648-79-0

Upstream product

• 100-42-5 styrene 
• 108-59-8 malonic acid dimethyl ester 
• 17851-98-8 1-phenyl-1-(tributylstannyloxy)ethene 
• 868-26-8 dimethyl 2-bromomalonate 
• 70-11-1 α-bromoacetophenone 
• 532-27-4 1-chloroacetophenone 
• 181265-77-0 2-bromoacetophenone t-butoxycarbonyl hydrazone 

Downstream Products

• 697287-90-4 dimethyl 2-(2-oxo-2-phenylethyl)-2-(prop-2-yn-1-yl)malonate 
• 1417578-82-5 dimethyl 2-(4-((tert-butyldimethylsilyl)oxy)but-2-yn-1-yl)-2-(2-oxo-2-phenylethyl)malonate 
• 1417578-52-9 (E)-dimethyl 2-(4-bromobut-2-en-1-yl)-2-(2-oxo-2-phenylethyl)malonate 
• 1417578-57-4 dimethyl 2-(4-bromobut-2-yn-1-yl )-2-(2-oxo-2-phenylethyl)malonate 
• 25333-24-8 3-benzoylpropionic acid methyl ester 

Relevant academic research and scientific papers

Novel synthesis of dihydropyrans and 2,8-dioxabicylo[3.3.0]oct-3-enes using Mn(III)-based oxidative cyclization

The Mn(III)-based reaction of 1,1-disubstituted alkenes with 2-(2-oxoethyl)malonates and 3-acetylpentane-1,4-diones gave novel substituted dihydropyrans and 2,8-dioxabicyclo[3.3.0]oct-3-enes in good yields, respectively. These routes rely on the nucleophi

Addition of malonic esters to azoalkenes generated in situ from α-bromo- and α-chlorohydrazones

Michael addition of malonic esters to azoalkenes generated in situ from α-bromo- and α-chlorohydrazones was accomplished. Both aliphatic and aromatic substrates bearing different functional groups are tolerated. The use of a strong base (sodium hydride) for generation of azoalkenes and deprotonation of malonate was found to be essential for a successful coupling. Synthetic potential of the obtained β-hydrazonoalkylmalonates was demonstrated by their smooth conversion into five- and six-membered N-heterocycles, functionalized hydrazides, 2-(2-oxo-2-arylethyl)malonates and 2-arylethylmalonates.

TBAI/TBHP-Promoted Generation of Malonyl Radicals: Oxidative Coupling with Styrenes Leads to γ-Keto Diesters

A metal-free protocol for oxidative coupling of malonic esters with styrenes to form γ-keto diesters has been developed. Key to the success of this process is the generation of malonyl radicals from unfunctionalized malonic esters under organo-catalysis conditions with TBAI and TBHP. This process tolerates both terminal and internal olefins with diverse malonic esters. It provides a new green metal-free alternative to traditional metal mediated process for generation of malonyl radicals and there by γ-keto diesters.

Vinyl dihydropyrans and dihydrooxazines: Cyclizations of catalytic ruthenium carbenes derived from alkynals and alkynones

A novel synthesis of 2-vinyldihydropyrans and dihydro-1,4-oxazines (morpholine derivatives) from alkynals and alkynones has been developed. The cyclizations require a mild generation of catalytic ruthenium carbenes from terminal alkynes and (trimethylsilyl)diazomethane followed by trapping with carbonyl nucleophiles. Mechanistic aspects of the new cyclizations are discussed. Setting a trap: A novel synthesis of 2-vinyldihydropyrans and dihydro-1,4-oxazines (morpholine derivatives) from alkynals and alkynones has been developed. The cyclizations require a mild generation of catalytic ruthenium carbenes from terminal alkynes and (trimethylsilyl)diazomethane followed by trapping with carbonyl nucleophiles.

Asymmetric synthesis of highly substituted β-lactones through oxidative carbene catalysis with LiCl as cooperative lewis acid

The reaction of enals with β-diketones, β-ketoesters, and malonates bearing a β-oxyalkyl substituent at the α-position by oxidative NHC catalysis to provide highly substituted β-lactones is described. Reactions occur with excellent diastereo- and enantioselectivity. The organo cascade comprises two C-C bond formations and one C-O bond formation. Up to four contiguous stereogenic centers including two fully substituted stereocenters are formed in the cascade. Highly substituted β-lactones are generated by NHC catalysis of enals with β-diketones, β-ketoesters, and malonates bearing a β-oxyalkyl substituent at the α-position. LiCl acts as cooperative Lewis acid. The organocascade comprises two C-C bond formations and one C-O bond formation. Up to four contiguous stereogenic centers including two fully substituted stereocenters are formed with high diastereo- and enantioselectivity.

Ti/Pd bimetallic systems for the efficient allylation of carbonyl compounds and homocoupling reactions

The allylation, crotylation and prenylation of aldehydes and ketones with stable and easily handled allylic carbonates is promoted by a Ti/Pd catalytic system. This Ti/Pd bimetallic system is especially convenient for the allylation of ketones, which are infrequent substrates in other related protocols, and can be carried out intramolecularly to yield five- and six-membered cyclic products with good stereoselectivities. In addition, Ti/Pd-mediated reductions and Wuertz-type dimerisation reactions can be readily carried out from allyl carbonates and carboxylates.

Synthetic utility of stannyl enolates as radical alkylating agents

(Equation presented) The radical-initiated β-ketoalkylation of haloalkanes with tributylstannyl enolates is described. Stannyl enolates derived from aromatic ketones are reactive toward the homolytic β-ketoalkylation of simple haloalkanes as well as those activated by an electron-withdrawing group. The reactivity of stannyl enolates as radical alkylating agents can be utilized for an efficient three-component coupling reaction among stannyl enolates, haloalkanes, and electron-deficient alkenes.

Cerium(IV) ammonium nitrate mediated addition of dimethyl malonate to styrene: a remarkable reaction

Cerium(IV) ammonium nitrate mediated addition of dimethyl malonate to styrene afforded the products 3 and 4 (via 7) along with small amounts of 5 and 6.