61878-72-6

Upstream product

• 19980-41-7 (Z)-4-methyl-3-trimethylsilyloxy-2-pentene 
• 100-52-7 benzaldehyde 
• 77152-10-4 trimethyl[(1-isopropylpropenyl)oxy]silane 
• 565-69-5 ethyl isopropyl ketone 
• 4798-45-2 4-methyl-pent-1-en-3-ol 

Relevant academic research and scientific papers

Resurrecting the cornforth model for carbonyl addition: Studies on the origin of 1,2-asymmetric induction in enolate additions to heteroatom-substituted aldehydes

Further experimental support for the Cornforth model is obtained from a systematic study of aldol reactions between methyl-substituted E and Z enolates and α-oxygen-substituted aldehydes. The observed dependence of diastereofacial selectivity on enolate configuration in this case is more consistent with the Cornforth model than with the the polar Felkin-Anh model (see scheme; X=OR, NR2, Cl).

Tetranuclear BINOL-titanium complex in selective direct aldol additions

(Chemical Equation Presented) The extremely robust and water-stable tetranuclear complex Ti4(μ-BINOLato)6(μ3- OH)4 (1) catalyzes the direct aldol addition with high degrees of regioselectivity at the sterically more encumbered α-side of unsymmetrical ketones. The formation of quaternary stereocenters is described. Oxygen-containing ene components can also be used as starting material in these reactions. When used with aliphatic aldehydes, acetals 18 or acetals of aldol adducts 20 were observed. As few as 0.2 mol % loadings with this catalyst 1 were enough to complete the reactions. Mechanistical aspects of the reactions are discussed.

Mixed alkylamido aluminate as a kinetically controlled base

The mechanisms by which directed ortho metalation (DoM) and postmetalation processes occur when aromatic compounds are treated with mixed alkylamido aluminate i-Bu3Al(TMP)Li (TMP-aluminate 1; TMP = 2,2,6,6- tetramethylpiperidide) have been inve

Unusual highly regioselective direct aldol additions with a moisture-resistant and highly efficient titanium catalyst

The extremely robust and water-stable tetranuclear complex Ti 4(μ-BINOLato)6(μ3-OH)4 was found to catalyze the direct aldol addition with high regioselectivities at the more steric α-encumbered side of unsymmetr

From allylic alcohols to aldols through a new nickel-mediated tandem reaction: Synthetic and mechanistic studies

Nickel hydride type complexes have been successfully developed as catalysts for the tandem isomerization-aldolization reaction of allylic alcohols with aldehydes. Optimization of the reaction conditions has shown that a cocatalyst, such as MgBr2, has a very positive effect on the kinetics of the reaction and in the yields of aldols. Under such optimized conditions {[NiHCl(dppe)] + MgBr2 at 3-5 mol %)}, this reaction affords the aldols in good to excellent yields. It is a full-atom-economy-type reaction that occurs under mild conditions. Furthermore, it has a broad scope for the allylic alcohols and it is compatible with a wide range of aldehydes, including very bulky derivatives. The reaction is completely regioselective, but it exhibits a low stereoselectivity, except for allylic alcohols with a bulky substituent at the carbinol center. The use of chiral non-racemic catalysts was not successful, affording only racemic compounds. However, it was possible to use asymmetric synthesis for the preparation of optically active aldols. Various mechanistic studies have been performed using, for instance, a deuterated alcohol or a deuterated catalyst. They gave strong support to a mechanism involving first a transition-metal-mediated isomerization of the allylic alcohol into the free enol, followed by the addition of the latter intermediate onto the aldehyde in an "hydroxyl-carbonyl-ene" type reaction. These results confirm that allylic alcohols can be considered as new and useful partners in the development of the aldol reaction.

Efficient synthesis of B-iododialkyl- and B-alkyldiiodoboranes as their acetonitrile complexes: Application for the enolboration - Aldolization of ethyl ketones

A series of B-(iododialkyl)boranes and B-(alkyldiiodo)boranes have been readily synthesized as their MeCN complexes from the corresponding chloro- and bromoboranes by treatment with NaI or KI in MeCN. In the presence of EtN(i-Pr)2, the B-(cyclo

Use of boron enolates in water. The first boron enolate-mediated diastereoselective aldol reactions using catalytic boron sources

Highly diastereoselective aldol reactions in water using a catalytic amount of diarylborinic acid have been developed. The reactions proceeded smoothly in the presence of a small amount of an anionic surfactant and a Br?nsted acid. Water was the most suit

Catalytic use of a boron source for boron enolate mediated stereoselective aldol reactions in water

Use of boron enolates in water! Boron enolates can be generated and used for aldol reactions in water by using a catalytic amount of Ph2BOH (see scheme). This is the first example of a catalytic use of a boron enolates. The mechanism of the rea

Chiral Lewis acid catalysis in aqueous media. Catalytic asymmetric aldol reactions of silyl enol ethers with aldehydes in a protic solvent including water

Chiral copper(II)-catalyzed asymmetric aldol reactions of silyl enol ethers with aldehydes have been successfully carried out in a water-ethanol solution. The use of the protic solvent including water is essential in these reactions, and this report has proposed and demonstrated a new concept for solvents in catalytic asymmetric aldol reactions.

Catalytic asymmetric Mukaiyama aldol reactions in aqueous media

Chiral copper(II)-catalyzed asymmetric aldol reactions of silyl enol ethers with aldehydes (the Mukaiyama aldol reaction) have been performed in an ethanol-water solution. The use of the protic solvent including water is a key to achieve these reactions.