66684-75-1

Upstream product

• 110-89-4 piperidine 
• 104-55-2 3-phenyl-propenal 
• 105-53-3 diethyl malonate 
• 181023-31-4 9-((E)-Styryl)-7,10-dithia-cyclohepta[de]naphthalene-8,8-dicarboxylic acid diethyl ester 
• 14371-10-9 (E)-3-phenylpropenal 
• 631-22-1 diethyl dibromomalonate 
• 156462-94-1 2-((E)-Styryl)-naphtho[1,8-de][1,3]dithiine 
• 5256-74-6 1,3-diethyl 2-diazopropanedioate 
• 685-87-0 Diethyl 2-bromomalonate 
• 64-17-5 ethanol 
• 676551-01-2 2-((Z)-3-Phenyl-allylidene)-malonic acid 

Downstream Products

• 63082-55-3 diethyl (E)-cinnamyl malonate 
• 1158805-52-7 C₂₃H₂₆O₄ 
• 1158805-51-6 (E)-2-(3,3-diphenylprop-1-enyl)malonic acid diethyl ester 
• 924882-07-5 (E)-diethyl 2-(2'-phenyl)ethenylcyclopropane-1,1-dicarboxylate 

Relevant academic research and scientific papers

Divergent Rearrangements of Vinylcyclopropane into Skipped Diene and Cyclopentene: Mechanism, Scope, and Limitations

Vinylcyclopropanes are versatile intermediates in organic synthesis which undergo various rearrangements. We report a new rearrangement of vinylcyclopropane into skipped diene. A detailed mechanistic study revealed that this transformation involves regioselective ring-opening of the cyclopropane ring followed by 1,2-migration of one of the cyclopropane substituents. Interestingly, our investigations showed that skipped diene is the kinetic product of the process but formation of a more stable cyclopentene is also accessible. The fundamental understanding of the processes involved enabled the development of divergent methodologies allowing to obtain cyclopentene or skipped diene from vinylcyclopropane in a selective and controlled manner.

Copper-catalyzed regiodivergent 1,4-and 1,6-conjugate silyl addition to diendioates: Access to functionalized allylsilanes

A copper-catalyzed regioselective 1,4-and 1,6-conjugate addition of a silyl reagent to diendioates was established. Various 1,4-and 1,6-protosilylation products were obtained in good yields and with high regioselectivity via tuning the ligands used in the reactions. This protocol has provided a simple and efficient method for the synthesis of multisubstituted functionalized allylsilanes.

Palladium-Catalyzed Asymmetric 1,6-Addition of Diarylphosphines to Allylidenemalonates for Chiral Phosphine Synthesis

A pincer-palladium-catalyzed asymmetric 1,6-addition of diarylphosphines to allylidenemalonates has been developed for the synthesis of chiral allylic phosphines with up to 89% ee under mild conditions.

Ring-Opening of Vinylcyclopropane-1,1-dicarboxylates by Boronic Acids under Ligandless Palladium Catalysis in Neat Water

We report a highly efficient ring-opening reaction of vinylcyclopropanes by boronic acids in water, using palladium nanoparticles formed from Pd(OAc)2 under ligandless conditions. Unsubstituted vinylcyclopropanes provide linear addition products with high selectivity, while a switch in regioselectivity to branched products is observed for aryl-substituted vinylcyclopropanes.

Organocatalytic asymmetric annulation of 1,3-bis(alkoxycarbonyl)buta-1,3- dienes and aldehydes

Asymmetric organocatalytic annulation of E/Z isomeric mixtures of bis(alkyl carboxylate)buta-1,3-dienes and aldehydes has been realized via enamine catalysis. In the presence of α,α-diphenyl-2-pyrrolidinemethanol trimethylsilyl ether, excellent stereo- and enantioselectivities were achieved for a broad spectrum of substrates.

Asymmetric michael addition of ketones to alkylidene malonates and allylidene malonates via enamine - Metal lewis acid bifunctional catalysis

Novel enamine-metal Lewis acid bifunctional catalysts were successfully applied to the asymmetric Michael addition of ketones to alkylidene malonates, offering excellent stereoselectivity (up to >99% ee and >99:1 dr). The asymmetric Michael addition of ketones to allylidene malonates was also achieved.

Natural α-amino acid l-lysine-catalyzed knoevenagel condensations of α,β-unsaturated aldehydes and 1,3-dicarbonyl compounds

Knoevenagel condensations of α,β-unsaturated aldehydes and 1,3-dicarbonyl compounds were catalyzed by primary natural amino acid L-lysine. The reactions were carried out at room temperature in dimethylsulfoxide. It provides a facile entry to a wide variety of α,β,γ,δ- unsaturated dicarbonyl compounds. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.

A nBuLi-mediated, expeditious and stereoselective ring-opening rearrangement of (arylmethylene)cyclopropane-1,1-dicarboxylates

We report herein an nBuLi-mediated, expeditious, ring-opening rearrangement of (arylmethylene)cyclopropane 1,1-diesters to prepare 1,3-diene derivatives with good stereo-selectivity. The reaction mechanism has also been discussed.

A dimethylsulfonium methylide mediated highly regioselective olefination of conjugated polyolefin 1,1-dioates to conjugated polyene-2-yl-malonates and their applications in Diels-Alder reactions

The reactions between dimethylsulfonium methylide and 1,3-diene- or 1,3,5-triene-1,1-dioates under specific conditions enable the highly regioselective tandem ylide addition-eliminative olefination to provide 1,3-butadien-2-yl- or 1,3,5-hexatriene-2-yl-malonates. Alkylation at malonate methine carbon of 1,3-butadien-2-ylmalonates with a suitable alkyl halide having in-built functionalities for a dienophile generation led to quick assembly of precursors for type 2 intramolecular Diels-Alder reaction. Syntheses of functionalized bicyclo[n.3.1] alkenes (n=5 or 6) with the double bond at the bridgehead position have been achieved via the IMDA. An asymmetric version of this reaction has been developed using a MacMillan's imidazolidinone catalyst, which provided a bicyclo[5.3.1] alkene with very high enantioselectivity. In situ methylation at malonate methine carbon of 1,3,5-hexatriene-2-yl-malonates followed by intermolecular Diels-Alder reaction with N-methylmaleimide provided the cycloadduct with complete regiocontrol and high diastereoselectivity.

1,6-Conjugate addition of boronic acids to 2-allylidenemalonates

The addition of boronic acids to 2-allylidenemalonates under RhI or Pd2+ catalysis shows an enhanced selectivity for the 1,6-addition reaction in comparison with diunsaturated monoesters. In the case of the RhI-catalyzed addition, the position of the new C=C double bond in the final product can be tuned with the choice of the base to give vinylmalonates of alkylidenemalonates. Georg Thieme Verlag Stuttgart.