53646-91-6

Upstream product

• 1515-78-2 buta-1,3-dien-1-ylbenzene 
• 14371-10-9 (E)-3-phenylpropenal 
• 16939-57-4 (E)-buta-1,3-dienylbenzene 

Downstream Products

• 56139-59-4 4-oxo-4-phenyl-butyraldehyde 

Relevant academic research and scientific papers

A domino Kornblum-DeLaMare/aza-Michael reaction of 3,6-dihydro-1,2-dioxines and application to the synthesis of the ceramide transport inhibitor (±)-HPA-12

A Kornblum-DeLaMare/aza-Michael reaction of 3,6-dihydro-1,2-dioxines with primary and secondary amines has been developed which affords 4-hydroxy-3-aminoketones. The aza-Michael products were reduced using non-selective NaBH4/MeOH or diastereoselective (up to 92:8) SnCl4/NaBH4 conditions yielding (1R?,3S?)-3-amino-1,4-diols in up to 97% and 70% yield respectively. The major reduction product was converted in two steps to (±)-HPA-12, which is an inhibitor of the cytosolic ceramide transporting protein.

Continuous Endoperoxidation of Conjugated Dienes and Subsequent Rearrangements Leading to C-H Oxidized Synthons

We have investigated the continuous flow photooxidation of several conjugated dienes and subsequent rearrangement using a practical and safe continuous-flow homemade engineered setup. End-to-end approaches involving endoperoxidation, Kornblum-DeLaMare rearrangement, and additional rearrangements are comprehensively detailed with optimization, scope, and scale-up to obtain useful hydroxyenones, furans, and 1,4-dicarbonyl building blocks.

A biosynthetically inspired route to substituted furans using the Appel reaction: Total synthesis of the furan fatty acid F5

Appel reaction conditions have been harnessed to affect a mild biosynthetically inspired dehydration of endoperoxides to deliver multi-substituted electron rich furans. Unlike traditional dehydrative procedures, this method is metal and acid free, and can be achieved under redox neutral conditions. It is general for a range of aryl and alkyl substituted endoperoxides, and is functional group tolerant. Furthermore, this procedure has been used to deliver an effective total synthesis of the furan fatty acid (FFA) F5.

Practical evaluation of compact fluorescent lamps for dye-sensitized photooxidation reactions

Energy-efficient compact fluorescent lamps (CFL) have been evaluated as a light source for the sensitized generation of singlet oxygen used in the oxidation of 1,3-butadienes and furfural derivatives using a range of dyes including rose bengal, methylene

A concise route to β-cyclopropyl amino acids utilizing 1,2-dioxines and stabilized phosphonate nucleophiles

(Chemical Equation Presented) 1,2-Dioxines react with glycine-derived phosphonate nucleophiles via a multistep cascade reaction to give β-cyclopropyl amino acid derivatives in good yield with excellent control of the cyclopropane stereocentres. The cyclopropyl ketones were oxidized to the corresponding carboxylic esters using Baeyer-Villiger conditions. Standard deprotection protocols produced a series of known β-cyclopropyl amino acids that are selective and potent agonists or antagonists of the metabotropic glutamate receptors in excellent yields.

A new route to diastereonumerically pure cyclopropanes utilizing stabilized phosphorus ylides and γ-hydroxy enones derived from 1,2-dioxines: Mechanistic investigations and scope of reaction

A new chemical transformation for the construction of diversely functionalized cyclopropanes utilizing 1,2-dioxines and stabilized phosphorus ylides as the key precursors is presented. Through a series of mechanistic studies we have elucidated a clear understanding of the hitherto unknown complex relationship between 1,2-dioxines 1a-e, and their isomeric cis/trans γ-hydroxy enones (23 and 21a-e), cis/trans hemiacetals 24a-e, and β-ketoepoxides (e.g., 26), and how these precursors can be utilized to construct diversely functionalized cyclopropanes. Furthermore, several new synthetically useful routes to these structural isomers are presented. Key features of the cyclopropanation include the ylide acting as a mild base inducing the ring opening of the 1,2-dioxines to their isomeric cis γ-hydroxy enones 23a-e, followed by Michael addition of the ylide to the cis γ-hydroxy enones 23a-e and attachment of the electrophilic phosphorus pole of the ylide to the hydroxyl moiety, affording the intermediate 1-2λ5-oxaphospholanes 4 and setting up the observed cis stereochemistry between H1 and H3. Cyclization of the resultant enolate (30a or 30b), expulsion of triphenylphosphine oxide, and proton transfer from the reaction manifold affords the observed cyclopropanes in excellent diastereomeric excess. The utilization of Co(SALEN)2 in a catalytic manner also allows for a dramatic acceleration of reaction rates when entering the reaction manifold from the 1,2-dioxines. While cyclopropanation is favored by the use of ester-stabilized ylides, the use of keto- or aldo-stabilized ylides results in a preference for 1,4-dicarbonyl formation through a competing Kornblum-De La Mare rearrangement of the intermediate hemiacetals. This finding can be attributed to subtle differences in ylide basicity/nucleophilicity. In addition, the use of doubly substituted ester ylides allows for the incorporation of another stereogenic center within the side chain. Finally, our studies have revealed that the isomeric trans γ-hydroxy enones and the β-keto epoxides are not involved in the cyclopropanation process; however, they do represent an alternative entry point into this reaction manifold.

Electron-transfer Photochemistry of Endoperoxides

Derivatives of 1,2-dioxacyclohex-4-ene and 2,3-dioxabicyclooct-5-ene (endoperoxides, EPs) form EDA complexes with tetracyanoethylene (TCNE).The phenyl-substituted EPs 3a, 4a, 4b and 6 undergo electron-transfer-induced reactions when the EDA complexes are irradiated.Two types of reactions are observed depending on the ring system.Monocyclic EPs (3a, 4a and 4b) afford furan derivatives, possibly through the Criegee-type rearrangement, and dehydration, whereas the bicyclic EP 6 undergoes cycloreversion through the C-O bond cleavage.

SENSITIZED PHOTO-OXYGENATION OF ACYCLIC CONJUGATED DIENES

Sensitized photo-oxygenation of a wide variety of acyclic 1,3-dienes was investigated.The 1,4-cycloaddition of singlet oxygen to acyclic conjugated dienes was closely related to the thermal Diels-Alder reaction in stereospecificity, and steric and electronic effects of substituents.Reactivity order of singlet oxygen toward conjugated dienes and isolated C-C double bonds was exhibited as follows: trisubstituted monoolefins > 2-substituted 1,3-dienes > disubstituted mono-olefins.