289478-45-1

Upstream product

• 555-16-8 4-nitrobenzaldehdye 
• 78-94-4 methyl vinyl ketone 
• 292634-18-5 3-(chloromethyl)-4-hydroxy-4-(4'-nitrophenyl)-2-butanone 
• 203111-49-3 3-[hydroxy(4-nitrophenyl)methyl]but-3-en-2-one 

Downstream Products

• 1219505-47-1 C₁₈H₂₃N₂O₃⁽¹⁺⁾*Cl^(1-) 
• 1219505-44-8 C₁₇H₂₂N₃O₃⁽¹⁺⁾*Cl^(1-) 
• 1101197-90-3 (S)-3-methyl-4-(4'-nitrophenyl)butan-2-one 
• 1453805-66-7 (R)-3-methyl-4-(4'-nitrophenyl)butan-2-one 

Relevant academic research and scientific papers

Titanium(IV) chloride, zirconium(IV) chloride or boron trichloride and phosphine-promoted Baylis-Hillman reaction of aldehydes with α,β-unsaturated ketone

In the Baylis-Hillman reaction of aldehydes with an α,β-unsaturated ketone, the chlorinated compound 1 was obtained as the major product using tributylphosphine as a Lewis base in the presence of titanium(IV) chloride, zirconium(IV) chloride or boron tric

Enantiodivergence in the reduction of α-methyl and α-halomethyl enones by microorganisms

Enones (Z)-3-methyl-(Z)-3-chloromethyl- and (Z)-3-bromomethyl-4-R-3-buten- 2-one (R = n-pentyl, phenyl, 2′- and 4′-chlorophenyl, 3′- and 4′-nitrophenyl, 4′-methoxyphenyl) were synthesized and subjected to reduction by the microorganisms Saccharomyces cerevisiae andGeotrichum candidum. Whereas the bioreduction of 3-methy-4-R-3-buten-2-ones afforded the corresponding (S)-4-R-3-methybutan-2-ones, the bioreduction of 3-chloromethyl- and 3-bromomethyl-4-R-3-buten-2-ones afforded the corresponding (R)-4-R-3-methybutan-2-ones.

SN2' versus SN2 reactivity: Control of regioselectivity in conversions of Baylis-Hillman adducts

TiCl4-induced Baylis-Hillman reactions of α,β- unsaturated carbonyl compounds with aldehydes yield the (Z)-2-(chloromethyl) vinyl carbonyl compounds 5, which react with 1,4diazabicyclo[2.2.2]octane (DABCO), quinuclidine, and pyridines to give the allylammonium ions 6. Their combination with less than one equivalent of the potassium salts of stabilized carbanions (e.g. malonate) yields methylene derivatives 8 under kinetically controlled conditions (SN2' reactions). When more than one equivalent of the carbanions is used, a second SN2' reaction converts 8 into their thermodynamically more stable allyl isomers 9. The second-order rate constants for the reactions of 6 with carbanions have been determined photometrically inDMSO. With these rate constants and the previously reported nucleophilespecific parameters N and s for the stabilized carbanions, the correlation log k (20°C) = s(N + E) allowed us to calculate the electrophilicity parameters E for the allylammonium ions 6 (-19 a rate-determining addition step.

Amine and titanium (IV) chloride, boron (III) chloride or zirconium (IV) chloride-promoted Baylis-Hillman reactions

The Baylis-Hillman reactions of various aryl aldehydes with methyl vinyl ketone at temperatures below -20°C using Lewis acids such as titanium (IV) chloride, boron (III) chloride or zirconium (IV) chloride in the presence of a catalytic amount of selected

Titanium(IV) chloride and quaternary ammonium salt promoted Baylis-Hillman reaction

The Baylis-Hillman reaction of aldehydes with α,β-unsaturated ketones can be drastically affected by the reaction temperature and Lewis bases. When the reaction was carried out at -78°C using catalytic amounts of quaternary ammonium salts (R4N

Titanium(IV) chloride and oxy-compounds promoted Baylis-Hillman reaction

The Baylis-Hillman reaction of aryl aldehydes with α,β-unsaturated ketones in the presence of titanium(IV) chloride can be promoted by oxy-compounds at room temperature, although they are not as effective as amines, chalcogenides, or quaternary ammonium salts. The oxy-compounds can be simple alcohols, ethers, and ketones. For aryl aldehydes having a strong electron-withdrawing group on the phenyl ring such as nitrobenzaldehyde or p-trifluoromethylbenzaldehyde, the chlorinated compound 1 is obtained as the major product. However, for other aryl aldehydes, the elimination compound 3 was formed predominantly. We also found that TiCl4·2THF or TiCl4·2Et2O complex is very effective for this reaction to give the chlorinated products in high yields at low temperature. A plausible mechanism is proposed.

Reexamination of products and the reaction mechanism of the chalcogeno- Baylis-Hillman reaction: Chalcogenide-TiCl4-mediated reactions of electron- deficient alkenes with aldehydes

Reactions of p-nitrobenzaldehyde (4) with methyl vinyl ketone (5) were conducted in the presence of TiCl4 and dimethyl sulfide (3) or selenopyranone 6. When the raw product was purified by column chromatography on silica gel, α-chloromethyl aldol 8 was obtained as a mixture of diastereoisomers 8a and 8b. In contrast, purification of the raw product by preparative TLC on silica gel gave α-methylene aldol 7. The mechanism for the formation of α-chloromethyl aldol 8 and diasteroselection for the syn- isomer 8a and anti-isomer 8b are discussed. (C) 2000 Elsevier Science Ltd.

Amendment in titanium(IV) chloride and chalcogenide-promoted Baylis- Hillman reaction of aldehydes with α,β-unsaturated ketones

The Baylis-Hillman reaction can be drastically affected by the reaction temperature and Lewis base. When the reaction was carried out at -20°C using methyl sulfide as a Lewis base in the presence of titanium(IV) chloride, the chlorinated compound 1 was