106353-47-3

Upstream product

• 66536-78-5 (+)-(R)-1-(p-tolylsulfinyl)-2-propanone 
• 123-38-6 propionaldehyde 
• 97169-20-5 N,N-Dimethyl-N'-[1-methyl-2-((R)-toluene-4-sulfinyl)-eth-(E)-ylidene]-hydrazine 
• 67-64-1 acetone 
• 189456-20-0 (R)-(E)-3-hexen-2-ol 
• 197306-87-9 (R)-(-)-(Z)-3-hexen-2-ol 

Relevant academic research and scientific papers

Complete Switch of Reaction Specificity of an Aldolase by Directed Evolution In Vitro: Synthesis of Generic Aliphatic Aldol Products

A structure-guided engineering of fructose-6-phosphate aldolase was performed to expand its substrate promiscuity toward aliphatic nucleophiles, that is, unsubstituted alkanones and alkanals. A “smart” combinatorial library was created targeting residues D6, T26, and N28, which form a binding pocket around the nucleophilic carbon atom. Double-selectivity screening was executed by high-performance TLC that allowed simultaneous determination of total activity as well as a preference for acetone versus propanal as competing nucleophiles. D6 turned out to be the key residue that enabled activity with non-hydroxylated nucleophiles. Altogether 25 single- and double-site variants (D6X and D6X/T26X) were discovered that show useful synthetic activity and a varying preference for ketone or aldehyde as the aldol nucleophiles. Remarkably, all of the novel variants had completely lost their native activity for cleavage of fructose 6-phosphate.

Contrasting steric effects of the ketones and aldehydes in the reactions of the diisopinocampheyl enolborinates of methyl ketones with aldehydes

Treatment of the diisopinocampheylborinates of a representative series of methyl ketones with a representative series of aldehydes, both of differing steric requirements provides aldols whose enantiomeric purifies depend on the steric requirements of both the ketones and the aldehydes. This study has shown that increasing the steric requirements of the R group in the ketones has a pernicious effect on the ee, while increasing the steric requirements of the R group in the aldehydes exerts a beneficial effect on the ee.

PalladiumdD-catalyzed exchange and isomerization reactions. 17. Exchange of chiral allyl alcohols with hydroxide, methoxide, and phenyl at high [Cl-]. Stereochemistry of the wacker reaction

At high [Cl ] (> 2.0 M), PdCl42- catalyzes the exchange of chiral allylic alcohols with hydroxy, methoxy, and phenyl to give chiral allyl-substituted olefins. With unsymmetrical olefins, isomerization occurs along with exchange. The hydroxyl exchange occurs in aqueous solution while the other exchanges are carried out in methanol solution. At low [Cl-] (0.1 M) oxidation to the corresponding β-hydroxy-, methoxy-, and phenyl-substituted carbonyl compounds occurred. The absolute configurations of the oxidation and exchange products should be the same if the same mode of addition to the Pd(II)-β-complex is operative. The absolute configurations of the oxidation and exchange products for the phenylation reaction were the same, while for hydroxy and methoxy they were different. This result indicates methanol and water must have different stereochemistries of addition at high and low [Cl-]. Thus, previous studies showing anti hydroxypalladation at high [Cl-] are not valid indicators of the stereochemistry at low [Cl-]. If anti addition occurs at high [Cl-], the addition must be syn at low [Cl-].

Preparation of Chiral β-Hydroxyketones by Aldol-type Condensation of Chiral p-Tolylsulfinylmethyl Ketones

Chiral β-hydroxyketones 7 with fair e.e. were prepared by treating newly prepared optically pure p-tolylsulfinylmethyl ketones 4 with t-butylmagnesium bromide and aldehydes 5 followed by desulfurization with aluminium amalgam.

C-C ASYMMETRIC BOND FORMATION MEDIATED BY OPTICALLY ACTIVE SULFOXIDES

Highly stereoselective C-C bond forming reactions can be performed with a variety of optically active sulfinyl derivatives to afford, after desulfurization, optically active sulfur-free products.