21136-48-1

Upstream product

• 94-41-7 benzalacetophenone 
• 762-72-1 allyl-trimethyl-silane 
• 3052-45-7 allyllithium 
• 106-95-6 allyl bromide 
• 614-47-1 1,3-diphenyl-propen-3-one 
• 130595-69-6 (E)-1,3-diphenylhexa-1,5-dien-3-ol 
• 14371-10-9 (E)-3-phenylpropenal 
• 591-51-5 phenyllithium 
• 556-56-9 allyl iodid 
• 107-05-1 3-chloroprop-1-ene 
• 1730-25-2 allylmagnesium bromide 
• 24850-33-7 allyltributylstanane 
• 104108-29-4 prenyl tributylstannane 
• 62668-02-4 (E)-1,3-diphenyl-2-propen-1-ol 

Downstream Products

• 53857-09-3 1,3-diphenyl-1,5-hexanedione 
• 72178-59-7 5-oxo-3,5-diphenylpentanal 
• 26274-35-1 2,4-diphenylpyridine 

Relevant academic research and scientific papers

Phosphazene bases and the anionic oxy-Cope rearrangement

Compounds containing a 1,5-hexadien-3-ol system undergo anionic oxy-Cope rearrangement when treated with the phosphazene super-base, P4-t-Bu. The [3,3] sigmatropic rearrangement occurs in hexane as well as in THF. The weaker phosphazene base, P

Tandem Anionic oxy-Cope Rearrangement/Oxygenation Reactions as a Versatile Method for Approaching Diverse Scaffolds

Tandem anionic oxy-Cope rearrangement/radical oxygenation reactions provide δ,?-unsaturated α-(aminoxy) carbonyl compounds, which serve as convenient precursors to diverse compound classes. Functionalized carbocycles are accessible by very rare all-carbon 5-endo-trig cyclizations, but also common 5-exo-trig radical cyclizations, based on the persistent radical effect. The tandem reactions can be further extended by highly diastereoselective allylation or reduction steps to give complex scaffolds.

Route to Highly Substituted Pyridines

Pyridine rings are common structural motifs found in a number of biologically active compounds, including some top-selling pharmaceuticals. We have developed a new approach to access substituted pyridines. The method aims to provide a reliable synthesis of a diverse range of substituted pyridines through a three-step procedure. Readily available enones are first converted into 1,5-dicarbonyls through a two-step Hosomi-Sakurai allylation/oxidative cleavage sequence, which is followed by subsequent cyclization to the corresponding pyridine using hydroxylamine hydrochloride. A variety of substituted pyridines have been synthesized using this method.

Base-mediated cascade rearrangements of aryl-substituted diallyl ethers

Two base-mediated cascade rearrangement reactions of diallyl ethers were developed leading to selective [2,3]-Wittig-oxy-Cope and isomerization-Claisen rearrangements. Both diaryl and arylsilyl-substituted 1,3-substituted propenyl substrates were examined, and each exhibits unique reactivity and different reaction pathways. Detailed mechanistic and computational analysis was conducted, which demonstrated that the role of the base and solvent was key to the reactivity and selectivity observed. Crossover experiments also suggest that these reactions proceed with a certain degree of dissociation, and the mechanistic pathway is highly complex with multiple competing routes.

Iron-Catalyzed Synthesis of C2 Aryl- and N-Heteroaryl-Substituted Tetrahydropyrans

An iron-catalyzed cyclization of hydroxy allylic derivatives into tetrahydropyrans possessing an N-heteroaryl at C2 is disclosed. The reaction proceeds with good yield and in high diastereoselectivity in favor of the more stable isomer. The diastereoselectivity results from an iron-induced reopening of the tetrahydropyrans, allowing a thermodynamic equilibration. The method allows access to a variety of 2,6-disubstituted as well as 2,4,6-trisubstituted tetrahydropyrans that could be considered as attractive scaffolds for the pharmaceutical industry.

Michael Addition of Soft Carbon Nucleophiles to Alkylidene Isoxazol-5-ones: A Divergent Entry to β-Branched Carbonyl Compounds

A novel, divergent strategy toward the synthesis of β-branched (and linear) carbonyl compounds is developed by taking advantage of alkylidene isoxazol-5-ones as key building blocks. The yields obtained range from good to excellent, therefore making the described methods attractive options for building such molecules. (Chemical Equation).

Stereoselective synthesis of side chain-functionalized tetrahydropyrans from 5-hexenols

Molecular oxygen stereoselectively converts 5-hexenols into 2,6-trans-, 2,5-trans-, and 2,4-cis-derivatives of 2-methyltetrahydropyran via oxidative cyclization/radical functionalization cascades, when activated by fluoro-substituted cobalt(II) bis-(β-diketonate) complexes in solutions of cyclohexa-1,4-diene (CHD). Aerobic 5-hexenol oxidations in solutions of bromotrichloromethane and CHD furnish products of 6-exo-bromocyclization, as exemplified by synthesis of diastereomerically pure 2,4,6-substituted tetrahydropyrans. The cobalt method extends to intermolecular alkene/alkanol cross-coupling and to multi-component reactions between dimethyl fumarate, CHD, a 5-hexenol, and dioxygen, providing α-tetrahydropyranyl-2-methyl succinates in synthetically useful yields.

Organocatalytic kinetic resolution via intramolecular aldol reactions: Enantioselective synthesis of both enantiomers of chiral cyclohexenones

Kinetic resolution of 6-aryl-2,6-hexanediones was achieved with chiral secondary amine catalyzed intramolecular aldolization. The current kinetic resolution protocol enables the synthesis of both enantiomers of cyclohexenones with moderate to good enantioselectivity. The Royal Society of Chemistry 2010.

Free radical-promoted conjugate addition of activated bromo compounds using titanocene(III) chloride as the radical initiator

Free radical-promoted conjugate addition of activated bromo compounds to α,β-unsaturated ketones and reactive α,β-unsaturated esters has been described using titanocene(III) chloride (Cp2TiCl) as the radical initiator. Cp2TiCl was prepared in situ from commercially available Cp2TiCl2 and activated zinc dust in THF.

Efficient Addition of Allylsilanes to α,β-Enones Using Catalytic Indium and Trimethylsilyl Chloride

α,β-Enones undergo an efficient Hosomi-Sakurai reaction with allyltrimethylsilane, in which a catalytic amount of indium is used in the presence of trimethylsilyl chloride as an activator under mild conditions to produce the conjugate addition products in good yields.