The highly regio- and enantioselective hydroxyamination of aldehydes with in situ generated nitrosocarbonyl compounds from a hydroxamic acid derivative was realized by simple and readily available chiral amine catalysts. The resulting hydroxyamination products were readily converted to the corresponding chiral 1,2-aminoalcohol or allylamine derivatives in one pot.
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http://dx.doi.org/10.1021/ol5000742 | DOI Listing |
Angew Chem Int Ed Engl
July 2017
Department of Chemistry, Binghamton University, Binghamton, NY, 13902, USA.
The rational design and implementation of enantiodivergent enamine catalysis is reported. A simple secondary amine catalyst, 2-methyl-l-proline, and its tetrabutylammonium salt function as an enantiodivergent catalyst pair delivering the enantiomers of α-functionalized aldehyde products in excellent enantioselectivities. This novel concept of designed enantiodivergence is applied to the enantioselective α-amination, aldol, and α-aminoxylation/α-hydroxyamination reactions of aldehydes.
View Article and Find Full Text PDFOrg Lett
March 2014
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan.
The highly regio- and enantioselective hydroxyamination of aldehydes with in situ generated nitrosocarbonyl compounds from a hydroxamic acid derivative was realized by simple and readily available chiral amine catalysts. The resulting hydroxyamination products were readily converted to the corresponding chiral 1,2-aminoalcohol or allylamine derivatives in one pot.
View Article and Find Full Text PDFJ Am Chem Soc
December 2013
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo , Kyoto 606-8502, Japan.
The first example of a highly regio- and enantioselective hydroxyamination of aldehydes with in situ generated nitrosocarbonyl compounds from hydroxamic acid derivatives was realized by combined use of TEMPO and BPO as the oxidant in the presence of a binaphthyl-modified amine catalyst.
View Article and Find Full Text PDFMolecules
February 2010
Organic Synthesis Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Patumwan, Bangkok 10330, Thailand.
Organocatalytic asymmetric alpha-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects and synthetic applications of alpha-oxidation, hydroxylation, aminoxylation, amination, hydrazination, hydroxyamination and related alpha-heteroatom functionalization of aldehydes, ketones and related active methylene compounds published during 2005-2009.
View Article and Find Full Text PDFJ Am Chem Soc
May 2006
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan.
A direct asymmetric hydroxyamination reaction of aldehydes with nitrosobenzene was found to be catalyzed by the novel axially chiral secondary amine catalyst (S)-1d. The resulting optically enriched hydroxyamination products were readily converted to beta-amino alcohols or 1,2-diamines in one pot.
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