771476-44-9

Upstream product

• 66-25-1 hexanal 
• 586-96-9 Nitrosobenzene 

Downstream Products

• 4938-52-7 (S)-Hept-1-en-3-ol 
• 1436-34-6 (S)-1,2-epoxyhexane 
• 1437789-15-5 (5R,9S)-7,7-diisopropyl-1-(4-methoxyphenyl)-5,9-divinyl-2,6,8-trioxa-7-silatridecane 
• 6920-22-5 (2S)-hexane-1,2-diol 

Relevant academic research and scientific papers

Total synthesis of umuravumbolide and hyptolide through silicon-tethered ring-closing metathesis

The total synthesis of umuravumbolide and hyptolide has been achieved in a efficient manner by using temporary silicon-tethered ring-closing metathesis and cross-coupling reactions as key steps. The stereogenic centres were generated by means of proline-catalysed α-aminoxylation of aldehydes and Brown's asymmetric allylation method. An efficient total synthesis of umuravumbolide and hyptolide has been achieved by using temporary silicon-tethered ring-closing metathesis. The stereogenic centres were generated by using asymmetric allyl boration and proline-catalysed α-aminoxylation with high degrees of enantioselectivity. Copyright

Bronsted acid assisted regio- and enantioselective direct o-nitroso aldol reaction catalysed by α,α-diphenylprolinol trimethylsilyl ether

In the presence of p-nitrobenzoic acid, the O-nitroso aldol reaction of nitrosobenzene with enolisable aldehydes may be promoted by commercially available α,α-diphenylprolinol trimethylsilyl ether. The reaction proceeds with good yields and essentially complete enantioselectivity, with catalyst loadings in the 510 mol % range. The resulting α-oxyaldehyde adducts may be transformed in situ into α-oxyimines, which provide 1,2-amino alcohols upon treatment with Grignard reagents, in good overall yield (45-59%) and with typical diastereomeric ratios ≥ 95:5.

Enantioselectivity switch in direct asymmetric aminoxylation catalyzed by binaphthyl-based chiral secondary amines

Binaphthyl-based amino acids (S)-1 and an aminosulfonamide (S)-2 were applied for direct asymmetric aminoxylation with nitrosobenzene. In the presence of either (S)-1 or (S)-2, the aminoxylation of aldehydes proceeded smoothly, and subsequent reduction wi

Direct asymmetric aminoxylation reaction catalyzed by a binaphthyl-based chiral amino sulfonamide with high catalytic performance

A binaphthyl-based amino sulfonamide (S)-2 was applied to the direct asymmetric aminoxylation of aldehydes with nitrosobenzene. The reaction catalyzed by (S)-2 proceeded smoothly to give the aminoxylated product in good yield with excellent enantioselectivity. This method represents a rare example of the highly enantioselective aminoxylation by a non-proline type catalyst with high catalytic performance.

Direct asymmetric aminoxylation reaction catalyzed by axially chiral amino acids

Binaphthyl-based amino acids were prepared and applied for the direct asymmetric aminoxylation of aldehydes with nitrosobenzene. The reaction catalyzed by (S)-1e proceeded smoothly to give the aminoxylated product in good yield and enantioselectivity. Thi

Highly enantioselective α-aminoxylation of aldehydes and ketones in ionic liquids

As the first example for the synthesis of optically active α-hydroxyaldehydes and α-hydroxyketones in ionic liquids, we applied RTILs into L-proline catalyzed direct enantioselective α-aminoxylation of both aldehydes and ketones successfully. This protoco

The direct catalytic asymmetric α-aminooxylation reaction: Development of stereoselective routes to 1,2-diols and 1,2-amino alcohols and density functional calculations

Proline-catalyzed direct asymmetric α-aminooxylation of ketones and aldehydes is described. The proline-catalyzed reactions between unmodified ketones or aldehydes and nitrosobenzene proceeded with excellent diastereo- and enantioselectivities. In all cases tested, the corresponding products were isolated with > 95% ees. Methyl alkyl ketones were regiospecifically oxidized at the methylene carbon atom to afford enantiomerically pure α-aminooxylated ketones. In addition, cyclic ketones could be α,α′-dioxidized with remarkably high selectivity, furnishing the corresponding diaminooxylated ketones with > 99% ees. The reaction mechanism of the proline-catalyzed direct asymmetric α-aminooxylation was investigated, and we performed density functional theory (DFT) calculations in order to investigate the nature of the plausible transition states further. We also screened other organocatalysts for the asymmetric α-oxidation reaction and found that several proline derivatives were also able to catalyze the transformation with excellent enantioselectivities. Moreover, stereoselective routes for the synthesis of monoprotected vicinal diols and hydroxyketones were found. In addition, short routes for the direct preparation of enantiomerically pure epoxides and 1,2-amino alcohols are presented. The direct catalytic α-oxidation is also a novel route for the stereoselective preparation of β-adrenoreceptor antagonists.