130296-61-6

Upstream product

• 2033-24-1 cycl-isopropylidene malonate 
• 622-47-9 4-tolylacetic acid 
• 104-87-0 4-methyl-benzaldehyde 
• 15795-51-4 2,2-dimethyl-5-(4-methylbenzylidene)-1,3-dioxane-4,6-dione 

Downstream Products

• 1026729-24-7 methyl 2-methylene-4-(4-methylphenyl)butanoate 
• 15795-51-4 2,2-dimethyl-5-(4-methylbenzylidene)-1,3-dioxane-4,6-dione 
• 130296-63-8 2,2,2',2'-Tetramethyl-5,5'-bis-(4-methyl-benzyl)-[5,5']bi[[1,3]dioxanyl]-4,6,4',6'-tetraone 

Relevant academic research and scientific papers

Traceless Electrophilic Amination for the Synthesis of Unprotected Cyclic β-Amino Acids

Electrophilic aminations involve an umpolung of a nitrogen atom, providing an alternate, distinctive synthetic strategy. The recent advent of various designed O-substituted hydroxylamines has significantly advanced this research field. An underappreciated

Simple, safe, large scale synthesis of 5-arylmethyl-2,2-dimethyl-1,3-dioxane-4,6-diones and 3-aryl-propanoic acids

Reaction of aryl aldehydes with Meldrum's acid 2 in the presence of formic acid and triethylamine with 5-arylmethyl Meldrum's acid derivatives 4 at room temperature, whereas at 80-100°C 3-arylpropanoic acids 5 are formed.

Asymmetric Alkoxy- and Hydroxy-Carbonylations of Functionalized Alkenes Assisted by β-Carbonyl Groups

As a fundamental type of carbonylation reaction, the alkoxy- and hydroxy-carbonylation of unsaturated hydrocarbons constitutes one of the most important industrial applications of homogeneous catalysis. However, owing to the difficulties in controlling multi-selectivities for asymmetric hydrocarbonylation of alkenes, this reaction is typically limited to vinylarenes and analogues. In this work, a highly efficient asymmetric alkoxy- and hydroxy-carbonylation of β-carbonyl functionalized alkenes was developed, providing practical and easy access to various densely functionalized chiral molecules with high optical purity from broadly available alkenes, CO, and nucleophiles (>90 examples, 84–99 % ee). This protocol features mild reaction conditions and a broad substrate scope, and the products can be readily transformed into a diverse array of chiral heterocycles. Control experiments revealed the key role of the β-carbonyl group in determining the enantioselectivity and promoting the activity, which facilitates chiral induction by coordination to the transition metal as rationalized by DFT calculations. The strategy of utilizing an innate functional group as the directing group on the alkene substrate might find further applications in catalytic asymmetric hydrocarbonylation reactions.

Facile Hydrogenolysis of C(sp3)–C(sp3) σ Bonds

The modification of benzylic quaternary, tertiary, and secondary carbon centers through palladium-catalyzed hydrogenolysis of C(sp3)–C(sp3) σ bonds is presented. When benzyl Meldrum's acid derivatives bearing quaternary benzylic centers are treated under mild hydrogenolysis conditions – palladium on carbon and atmospheric pressure of hydrogen – aromatics substituted with tertiary benzylic centers and Meldrum's acid are obtained with good to excellent yield. Analogously, substrates containing tertiary or secondary benzylic centers yield aromatics substituted with secondary benzylic centers or toluene derivatives, respectively. Furthermore, this strategy is used for the high yielding synthesis of diarylmethanes. The scope of the reductive dealkylation reaction is explored and the limitations with respect to steric and electronic factors are determined. A mechanistic analysis of the reaction is described that consisted of deuterium labelling experiments and hydrogenolysis of enantioenriched derivatives. The investigation shows that the C(sp3)–C(sp3) σ bond-cleaving events occur through a hybrid SN1/SN2 mechanism, in which the palladium center displaces a carbon-based leaving group, namely Meldrum's acid, with inversion of configuration, followed by reductive elimination of palladium to furnish a C?H bond. (Figure presented.).

High-yielding sequential one-pot synthesis of chiral and achiral α-substituted acrylates via a metal-free reductive coupling reaction

A general process for the high-yielding synthesis of substituted chiral and achiral α-substituted acrylates was achieved through the sequential one-pot combination of a metal-free reductive coupling reaction followed by an Eschenmoser methylenation. The proline catalyzed reaction of Meldrum's acid, aldehydes and Hantzsch ester followed by methylenation was successful with Eschenmoser's salt in the presence of an alcohol solvent. Herein, we have shown the high-yielding synthesis of privileged building blocks from chiral/achiral α-substituted acrylates and shown them to be very good intermediates in the pharmaceuticals and natural products synthesis. This journal is the Partner Organisations 2014.

A practical synthesis of α-substituted tert-butyl acrylates from meldrum's acid and aldehydes

An expeditious synthesis of α-substituted tert-butyl acrylates from commercially available aldehydes and Meldrum's acid has been established. The method benefits from a telescoped condensation-reduction sequence to afford 5-monosubstituted Meldrum's acid

A novel and green protocol for two-carbon homologation: A direct amino acid/K2CO3-catalyzed four-component reaction of aldehydes, active methylenes, Hantzsch esters and alkyl halides

A novel and green approach for the two-carbon homologation of aldehydes using amino acid catalysis has been developed and further extended to the generation of pharmaceutically active cyano-esters via four-component reactions in one-pot.

One Pot Synthesis of Monoalkylated and Mixed, Dialkylated Meldrum's Acid Derivatives

A simple one pot method, involving sequential Knoevenagel condensation of Meldrum's acid with aromatic aldehydes, conjugate reduction of ylidene Meldrum's acid using sodium borohydride followed by alkylation, to prepare mixed dialkylated derivatives of Meldrum's acid is described.

Process for the preparation of 1,3-dioxane-4,6-dione derivates

The invention relates to a process for preparing the compounds of general formula (I), wherein Rmeans hydrogen, C1 4alkyl or (C1 5alkoxy)carbonyl group; R1stands for a C1 6 alkyl, (C1 5alkyl)carbonyl, (C1 5alkoxy)carbonyl or (C1 5alkoxy)carbonyl-(C1 4alkyl) group; or a cyclohexyl group; or a cyclopentyl group; or a phenyl, furyl or thienyl group, optionally substituted, or a b-CH=CH group, wherein b is a phenyl group; or R and R1together form a C4 5alkylene group; R2represents a C1 5alkyl or phenyl group; R3means hydrogen or a C1 4alkyl group; or R2 and R3together form a pentylene group. By reacting a compound of general formula (II) with a compound of general formula (III) and/or reducing a compound of the general formula (IV),

Reduction of substituted isopropylidene methylenemalonates using borohydride exchange resin

Substituted isopropylidene methylenemalonates (Knovenagel type products) (1-7) derived from Meldrum's acid (2,2-dimethyl-1,3-dioxan-4,6-dione) are readily reduced by borohydride exchange resin under mild reaction conditions to give 8-14 in high yields and