53777-08-5

Upstream product

• 557-18-6 diethylmagnesium 
• 98-86-2 acetophenone 
• 135-98-8 sec-Butylbenzene 
• 557-20-0 diethylzinc 
• 544-97-8 dimethyl zinc(II) 
• 93-55-0 1-phenyl-propan-1-one 
• 1565-75-9 2-phenyl-2-butanol 
• 925-90-6 ethylmagnesium bromide 
• 1240815-92-2 (R)-4,4,5,5-tetramethyl-2-(2-phenylbutan-2-yl)-1,3,2-dioxaborolane 
• 73798-17-1 (SS)-1-(N-methylphenylsulfonimidoyl)-2-phenyl-2-butanol 
• 10467-10-4 ethylmagnesium iodide 
• 75-16-1 methylmagnesium bromide 
• 116652-87-0 (2R)-1-((S)-2-methoxymethylpyrrolidino)-2-phenyl-2-propanol 
• 116652-85-8 α-((S)-2-methoxymethylpyrrolidino)acetophenone 

Downstream Products

• 51586-24-4 1-amino-2,2,2-trifluoro-1-phenylethane 
• 820961-80-6 (S)-1-methyl-1-phenylpropyl diphenylphosphinite 

Relevant academic research and scientific papers

Asymmetric synthesis of tertiary vinyl carbinols by highly stereoselective methylation of α-methyl-β-ketosulfoxides with aluminum reagents

Methylation of chiral acyclic α-methyl-β-ketosulfoxides with Me3Al and Me2AlCl is reported. Induced configuration at hydroxylic carbon is mainly controlled by the configuration of the sulfinyl group, with de's higher than 90% in most of the cases regardless the configuration at C-α. The stereochemical pathway seems to be different with both reagents, thus affording a higher stereoselectivity with Me 2AlCl. Pyrolytic desulfinylation and hydrogenolysis of the C-S bond allowed the transformation of the resulting hydroxysulfoxides into interesting optically pure tertiary methyl carbinols.

Harnessing the Power of the Asymmetric Grignard Synthesis of Tertiary Alcohols: Ligand Development and Improved Scope Exemplified by One-Step Gossonorol Synthesis

A series of N-substituted cyclohexyldiaminophenolic ligands for the asymmetric Grignard synthesis of tertiary alcohols is reported. The 2,5-dimethylpyrrole-decorated ligand led to improved enantioselectivities and broadened the scope of the methodology. As an exemplar, we report an unprecedented highly selective one-step synthesis of gossonorol in 93% ee, also constituting the shortest formal syntheses of natural products boivinianin B and yingzhaosu C.

Very short highly enantioselective Grignard synthesis of 2,2-disubstituted tetrahydrofurans and tetrahydropyrans

Phenones with elongated chains are shown to be excellent substrates for ligand-promoted asymmetric Grignard synthesis of tertiary alcohols. In turn this enables the simple, short and highly enantioselective (up to 96% ee) preparation of chiral 2,2-disubst

Asymmetric Grignard Synthesis of Tertiary Alcohols through Rational Ligand Design

A simple, general and practical method is reported for highly enantioselective construction of tertiary alcohols through the direct addition of organomagnesium reagents to ketones. Discovered by rational ligand design based on a mechanistic hypothesis, it has an unprecedented broad scope. It utilizes a new type of chiral tridentate diamine/phenol ligand that is easily removed from the reaction mixture. It is exemplified by application to a formal asymmetric synthesis (>95:5 d.r.) of vitamin E.

CHIRAL DIAMINE COMPOUNDS FOR THE PREPARATION OF CHIRAL ALCOHOL AND CHIRAL AMINE

A process for the stereoselective preparation of a chiral alcohol or a chiral amine, the process comprising reacting a first prochiral reactant selected from the group consisting of a ketone, an aldehyde, and an inline, with a second reactant comprising a Grignard reagent, in the presence of a chiral trans-diamim of formula (1) as defined herein. Also provided is the use of the chiral trans-diamine of formula (1) in a Grignard reaction and the chiral trans-diamines per se.

QSAR analysis of the catalytic asymmetric ethylation of ketone using physical steric parameters of chiral ligand substituents

We have demonstrated that a validated QSAR (quantitative structure-activity relationship) model can be constructed between sterimol steric parameters of the N-substituents of chiral 1,2-amino-phosphoramide ligands and the enantiomeric ratios of alcohol products produced in the asymmetric additions of diethylzinc to acetophenone, which is powerful for predicting the steric effects of ligand substituents on enantioselectivities and instructive for ligand optimization.

Molecular and Merrifield supported chiral diamines for enantioselective addition of ZnR2 (R = Me, Et) to ketones

Chiral 1,2-ethylenediamines have been previously reported as active catalysts in the enantioselective addition reactions of ZnR2 to either methyl- or trifluoromethyl-ketones. Subtle changes in the molecular structure of different catalysts are described herein and lead to a dramatic effect in their catalytic activity. From these findings, we demonstrate the selective reactivity of the ligands used in the addition of ZnR2 (R = Me, Et) to methyl- and trifluoromethyl-ketones offering an enantioselective access either to chiral non-fluorinated alcohols or to chiral fluorinated tertiary alcohols. Considering the importance of the chiral trifluoromethyl carbinol fragment in several biologically active compounds, we have extended the scope of the addition reaction of ZnEt2 to several trifluoromethylketones catalyzed by (R,R)-1,2-diphenylethylenediamine derivatives. This work explores a homogeneous approach that provides excellent yields and very high ee and the use of a heterogenized tail-tied ligand affording moderate ee, high yields and allowing an easier handling and recycling.

New ligands and structural insights into the catalytic asymmetric addition of organozinc reagents to ketones

The catalytic asymmetric addition of alkyl groups to ketones has received considerable attention. Outlined herein is the synthesis of two new ligands based on the C2-symmetric 11,12-diamino-9,10-dihydro-9,10- ethanoanthracene. The scope of the new ligands has been evaluated in the catalytic asymmetric addition of diethylzinc to a variety of ketones. Enantioselectivities as high as 99% have been achieved. The structures of two of these ligands have been determined by X-ray crystallography and are compared with related structures. Additionally, the structure of a titanium complex bound to a bis(sulfonamide) diol ligand is reported.

Commercially available neat organozincs as highly reactive reagents for catalytic enantioselective addition to ketones and aldehydes under solvent free conditions

Neat Et2Zn, Ph2Zn, and highly concentrated Me 2Zn are highly reactive organozinc reagents, which are commercially available in bulk quantities. We here report a catalytic enantioselective Et2Zn, Ph2Zn, and Me2Zn addition to ketones and aldehydes under solvent free or highly concentrated conditions without Ti(Oi-Pr)4 as a conventional activator of organozinc reagents. The desired optically active tertiary and secondary alcohols were obtained in good yield with high enantioselectivity when compared to the conventional solvent-use conditions. From the viewpoint of ecological and environmental reasons in green chemistry, this catalysis would be practical for not only academic but also industrial use.

Full chirality transfer in the conversion of secondary alcohols into tertiary boronic esters and alcohols using lithiation-borylation reactions

New conditions, full transfer: Using MgBr2/MeOH as an additive now provides essentially 100 % retention of configuration in the lithiation-borylation reaction, thus leading to tertiary boronic esters (or tertiary alcohols) with exceptionally hi