74676-21-4

Upstream product

• 100-52-7 benzaldehyde 
• 814-75-5 3-bromo-butanone 
• 78-93-3 butanone 
• 78-94-4 methyl vinyl ketone 
• 30719-18-7 3-iodo-butan-2-one 
• 598-32-3 2-hydroxy-3-butene 
• 13787-35-4 Tri-tert-butyl-stibane 
• 81435-38-3 2-methyl-1-phenyl-4-trimethylsilyl-3-butyn-1-ol 
• 1056477-06-5 2-bromocyclohexanone 
• 4091-39-8 3-chloro-2-butanone 
• 1024022-46-5 1-hydroxy-2-methyl-1,1-diphenyl-3-butanone 
• 570385-31-8 (Z)-trichloro[(1-methylpropenyl)oxy]-silane 
• 783-08-4 [4-(benzylideneamino)phenyl]methanol 
• 153737-63-4 (CH₃CH₂CH₂CH₂)3SnOC(CH₃)CHCH₃ 

Downstream Products

• 924637-68-3 (1S,2S,3S)-2-methyl-1-phenylbutane-1,3-diol 
• 283151-73-5 [1S,2R,3S]-(+)-2-methyl-1-phenyl-1,3-butanediol 
• 283151-79-1 [1S,2S,3R]-(+)-2-methyl-1-phenyl-1,3-butanediol 

Relevant academic research and scientific papers

A new selective allyl transfer reagent: Facile entry to β-hydroxy enol silyl ethers bearing two contiguous stereogenic centers

η3-Allyltitanium(III) complexes functionalized on the C-2 with a silyloxy group can be prepared by the reaction of titanocene dichloride with isopropylmagnesium chloride in the presence of the corresponding 2-silyloxybutadienes. These complexes undergo a highly regio- and diastereoselective addition with aldehydes to produce, depending on the treatment applied, anti diastereomeric β-hydroxy silyl enol ethers or β-hydroxy ketones. Two defined contiguous stereocenters make the enol silyl ethers containing them versatile synthons for further stereocontrolled transformations. The reaction constitutes a new method for directing electrophiles to the α-position of the α,β-enone system.

Intraparticle Diffusional versus Site Effects on Reaction Pathways in Liquid-Phase Cross Aldol Reactions

Chemo- and regioselectivity in a heterogeneously catalyzed cross aldol reaction were directed by tuning the nature of the sites, textural properties, and reaction conditions. Catalysts included sulfonic acid-functionalized resins or SBA-15 with varying particle size or pore diameter, H-BEA zeolites, and Sn-BEA zeotype; conditions were 25 °C to 170 °C in organic media. Benzaldehyde and 2-butanone yielded branched (reaction at -CH2- of butanone) and linear (reaction at -CH3) addition and condensation products; and fission of the branched aldol led to β-methyl styrene and acetic acid. Strong acids promoted the dehydration step, and regioselectivity originated from preferred formation of the branched aldol. Both, resins and functionalized SBA-15 materials yielded predominantly the branched condensation product, unless particle morphology or temperature moved the reaction into the diffusion-limited regime, in which case more fission products were formed, corresponding to Wheeler Type II selectivity. For H-form zeolites, fission of the branched aldol competed with dehydration of the linear aldol, possibly because weaker acidity or steric restrictions prevented dehydration of the branched aldol.

A catalytic aldol reaction and condensation through in situ boron "ate" complex enolate generation in water

(Chemical Equation Presented) Cooperation is key: N-Butyl-1-benzimidazole- 2-phenylboronic acid hydroxide complex catalyzes the aldol condensation and aldol addition between hydroxyacetone or acetone, and different aldehydes in water. The catalytic activity results from cooperative interactions between the boronate complex and the imidazole function. Aldol condensation gives the unsaturated methyl ketones of acetone, whereas aldol addition predominates with hydroxyacetone.

Generation of rhodium enolates via retro-aldol reaction and its application to regioselective aldol reaction

Retro-aldol reactions of β-hydroxy ketones take place under rhodium catalysis, leading to regioselective formation of the corresponding rhodium enolates. The enolates react with aldehydes in situ to afford the corresponding aldol adducts in high yields.

Highly diastereo- and enantioselective direct aldol reactions of aldehydes and ketones catalyzed by siloxyproline in the presence of water

Proline-based organocatalysts have been developed for a highly enantioselective, direct aldol reaction of aldehydes and ketones in the presence of water. While several surfactant-proline combined catalysts have proved effective, proline derivatives with a hydrophobic moiety such as rraw-siloxy-L-proline and cis-siloxy-D-proline, both of which are easily prepared from the same commercially available 4-hydroxy-L-proline. have been found to be the most effective organocatalysts examined in this study, affording the aldol product with excellent diastereo- and enantioselectivities, these two catalysts generating opposite enantiomers. Water affects the selectivity, and poor results are obtained under neat reaction conditions or in dry organic solvents. More than three equivalents of water are required for the best diastereo- and enantioselectivities. while three equivalents is the recommended amount from a synthetic point of view. The reaction proceeds in the organic phase, and also proceeds in the presence of a large amount of water. The large-scale preparation of aldols with the minimal use of an organic solvent, including in the purification step. is described.

Direct aldol and tandem Mannich reactions in room temperature ammonia solutions

An economical, simple, and efficient direct aldol reaction via the double activation of both aldehydes and ketones by ammonia has been developed. An unprecedented tandem Mannich reaction was observed when hydroxybenzaldehydes, pyrrole-2-carboxyaldehyde, a

Indium(III) acetate-catalyzed 1,4-reduction and reductive aldol reactions of α-enones with phenylsilane

A catalytic amount of In(OAc)3 smoothly promoted 1,4-reduction of certain α-enones with PhSiH3 in ethanol at ambient temperature. The intermediary enolates could be used for inter- and intramolecular aldol reactions and intramolecular Michael addition.

Ruthenium-catalyzed tandem olefin migration/aldol and Mannich-type reactions in water and protic solvents

Cross-coupling between 3-buten-2-ol (2) and aldehyde in the presence of a catalytic amount of [RuCl2(PPh3)3] has been developed, through a tandem olefin migration/aldol reaction in a water/toluene mixture. The presence of

Stereoselective aldol additions of achiral ethyl ketone-derived trichlorosilyl enolates

Methods for the preparation of geometrically defined enoxy(trichlorosilanes) derived from ethyl ketone enolates have been developed. The addition of enoxy(trichlorosilanes) (trichlorosilyl enolates) to aldehydes proceeds with good yields in the presence of catalytic amounts of chiral phosphoramides. The reaction of Z-trichlorosilyl enolates to aryl aldehydes affords aldol products with good to excellent diastereo- and enantioselectivities. Phosphoramide-catalyzed aldol additions lacked substrate generality providing modest selectivities with unsaturated and aliphatic aldehydes. In all cases, the phosphoramide-catalyzed aldol addition of E-trichlorosilyl enolates to aldehydes provided good yields with moderate to good stereoselectivities.

Preparation of organomanganese reagents from organic halides with activated manganese

Reduction of Li2MnCl4 with magnesium metal provided activated manganese as a black suspension in THF. Treatment of organic halides such as allyl bromides, α-halo esters or aryl halides with activated manganese furnished various organomanganese reagents which reacted further with electrophiles to afford the corresponding adducts. The reaction of a ketone bearing an iodoaryl moiety with this active manganese induced cyclization to provide dihydroindene derivative.